logo
CONTENT TYPES

COVID-19 Remote Access Support:

Learn More about expanded access to ACS Publications research.

Iron-Catalyzed/Mediated C–N Bond Formation: Competition between Substrate Amination and Ligand Amination

  • Suman Sinha
    Suman Sinha
    Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur Botanic Garden, Howrah 711103, India
    More by Suman Sinha
  • Rina Sikari
    Rina Sikari
    Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur Botanic Garden, Howrah 711103, India
    More by Rina Sikari
  • Vivek Sinha
    Vivek Sinha
    Homogeneous Catalysis Group, van’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands
    More by Vivek Sinha
  • Upasona Jash
    Upasona Jash
    Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur Botanic Garden, Howrah 711103, India
    More by Upasona Jash
  • Siuli Das
    Siuli Das
    Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur Botanic Garden, Howrah 711103, India
    More by Siuli Das
  • Paula Brandão
    Paula Brandão
    Departamento de Química, CICECO-Instituto de Materiais de Aveiro, Universidade de Aveiro, 3810-193 Aveiro, Portugal
  • Serhiy Demeshko
    Serhiy Demeshko
    Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, D-37077 Göttingen, Germany
  • Franc Meyer
    Franc Meyer
    Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, D-37077 Göttingen, Germany
    More by Franc Meyer
  • Bas de Bruin
    Bas de Bruin
    Homogeneous Catalysis Group, van’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands
    More by Bas de Bruin
  • Nanda D. Paul*
    Nanda D. Paul
    Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur Botanic Garden, Howrah 711103, India
    *E-mail: [email protected].
Cite this: Inorg. Chem. 2019, 58, 3, 1935-1948
Publication Date (Web):January 14, 2019
https://doi.org/10.1021/acs.inorgchem.8b02877
Copyright © 2019 American Chemical Society
Subscribed Access
Article Views
1359
Altmetric
-
Citations
LEARN ABOUT THESE METRICS

Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.

PDF (3 MB)
Supporting Info (1)»

Abstract

Iron catalyzed carbon–nitrogen bond formation reactions of a wide variety of nucleophiles and aryl halides using well-defined iron-complexes featuring redox noninnocent 2-(arylazo)-1,10-phenanthroline (L1) ligands are reported. Besides substrate centered C–N coupling, C–N bond formation reactions were also observed at the ortho- and para-positions of the phenyl ring of the coordinated azo-aromatic scaffolds affording new tetradentate ligands, 2-N-aryl-(2-arylazo)-1,10-phenanthroline (L2), and tridentate ligands, 4-N-aryl-(2-arylazo)-1,10-phenanthroline (L3), respectively. Control experiments and mechanistic studies reveal that the complex [FeL1Cl2] (1) undergoes in situ reduction during the catalytic reaction to produce the monoanionic complex [1], which then acts as the active catalyst. The metal (iron) and the coordinated ligand were found to work in a cooperative manner during the transfer processes involved in the fundamental steps of the catalytic cycle. Detailed experimental and theoretical (DFT) studies were performed to get insight into the competitive substrate versus ligand centered amination reactions.

Synopsis

Iron catalyzed C−N cross coupling reactions of a wide range of nucleophiles and aryl halides using well-defined iron-complexes featuring redox noninnocent 2-(arylazo)-1,10-phenanthroline (L1) ligands are reported. In addition to substrate centered C−N coupling, competing C−N coupling reactions were also observed at the ortho- and para-positions of the phenyl ring of the coordinated azo-aromatic ligands affording new tetradentate azo-aromatic ligands, 2-N-aryl-(2-arylazo)-1,10-phenanthroline (L2), and tridentate azo-aromatic scaffolds, 4-N-aryl-(2-arylazo)-1,10-phenanthroline (L3), respectively. Mechanistic studies suggest that the complex 1 undergoes reduction in situ during the catalytic reaction to produce the monoanionic complex [1], which then acts as the active catalyst. Both metal (iron) and the coordinated ligand participate in a cooperative manner during electron transfer processes involved in the elementary steps of the catalytic cycle.

Introduction

ARTICLE SECTIONS
Jump To

Construction of C–N bonds is one of the important challenges in organic synthesis due to the widespread presence of nitrogen-containing compounds in a broad spectrum of synthetic and natural organic molecules.(1) Notable progress has been made in developing catalytic and stoichiometric C–N bond forming reactions. Numerous synthetic methods including both metal catalyzed and classical organic reactions were developed for carbon–nitrogen bond formation via direct functionalization of C–X (X: H, halides, pseudo halides, etc.) bonds.(2−6) However, most of the metal catalyzed C–N bond formation reactions were successfully achieved using the scarce and relatively expensive noble metal based catalysts such as palladium,(3) rhodium,(4) or ruthenium.(5) Therefore, achieving C–N cross coupling reactions using cheap and easily accessible catalysts based on 3d-base metals is desirable.
Consequently, worldwide extensive research efforts are undertaken to develop new strategies for the formation of C–N bonds using cheap and earth abundant base metals as alternatives to the expensive heavy metals like palladium, rhodium, or ruthenium. However, base metals tend to undergo one-electron oxidation changes, and the subsequent two-electron transfer processes are mostly thermodynamically unfavorable and hence require elevated temperatures. For example, several reported C–N coupling reactions, catalyzed by earth-abundant and cheap Cu and Ni-catalysts, require high temperatures for the reaction to proceed.(6,7) It is worth mentioning here that copper catalysts are very efficient and even produce the desired C–N coupled products in high yield with ppm level catalyst loading.
In this perspective, the catalytic applications of transition metal complexes featuring redox noninnocent scaffolds are of growing interest.(8) Redox noninnocent ligands, other than offering coordination to transition metal ions, can participate in electron transfer processes during different elementary steps of any chemical transformations and thus enable the catalyst to avoid high energy metal centered redox events.(8) In recent times, Chirik and co-workers reported several catalytic reactions such as hydroboration, hydrosilylation, cycloaddition using base metal complexes of redox noninnocent bis(imino)pyridine ligands. Both metal and the coordinated bis(imino)pyridine ligands were found to participate in a cooperative manner during these catalytic reactions (Scheme 1).(9) Using the redox noninnocent properties of diamine and aminophenol based ligand systems, several new catalytic and stoichiometric reactions were explored.(10) Using redox noninnocent carbene radical ligands, de Bruin and co-workers reported several cobalt-catalyzed chemical transformations.(11)

Scheme 1

Scheme 1. Different Chemical Transformations Using Iron Complexes of Redox Noninnocent Ligands
In contrast to the above-mentioned redox noninnocent ligand systems, the application of redox noninnocent azo-aromatic scaffolds in catalysis has been less studied even though their rich redox chemistry has been well established since long.(12) Because of the presence of vacant acceptor orbitals, this class of ligands can accept multiple electrons in their π* orbitals and thus can act as electron reservoir during catalytic reactions. Only in recent times, Goswami and co-workers reported catalytic alcohol oxidation reactions using nickel and zinc complexes featuring 2,6-bis(phenylazo)pyridine ligands as catalysts. The coordinated 2,6-bis(phenylazo)pyridine scaffold functions as an electron reservoir in these dehydrogenation reactions.(13)
Recently, we reported the synthesis and characterization of new redox active ligands, 2-(arylazo)-1,10-phenanthroline (L1) and their iron complexes.(14a) Out of these Fe(II)-complexes reported, the one electron reduced penta-coordinated complexes, [FeII{(L1a,b)•–}Cl2] ([1a], [1b]) were found to catalyze alcohol oxidation reactions. The coordinated 2-(arylazo)-1,10-phenanthroline (L1) scaffold as well as the iron-center was found to act in a synergistic manner during the catalytic reaction.(14a) In accordance to our current research to study new catalytic reactions using transition metal complexes of redox noninnocent ligands, we chose the one electron reduced penta-coordinated Fe(II)-complexes [FeII{(L1a-c)•–}Cl2] ([1a-c]) as catalysts to study catalytic C–N bond formation reactions between aryl halides and nitrogen nucleophiles (Scheme 2). Our intention was to (partly) use the ligand centered redox events during the catalytic turnover and thereby to avoid high-energy Fe-centered redox steps during different elementary steps of the catalytic reaction. Two new Fe(III)-complexes [FeIIILa/bCl3] (2a, 2b) were synthesized and also employed as catalyst to study the C–N coupling reactions. The low-cost and environmentally benign nature of iron further intrigued us to take up this work.

Scheme 2

Scheme 2. Synthesis of Catalysts 1a, 1b, 1c and 2a, 2b, 2c
Interestingly, other than the desired substrate centered amination, competitive C–N bond formation was also observed at the ortho- and para-positions of the coordinated azo-aromatic ligands (L1) affording new tetradentate ligands, 2-N-aryl-(2-arylazo)-1,10-phenanthroline (L2) and tridentate ligands, 4-N-aryl-(2-arylazo)-1,10-phenanthroline (L3), respectively (Figures 1 and 2; Scheme 3). Among the various nitrogen nucleophiles tested, when primary aromatic amines were used as the nucleophile under the optimized reaction conditions, a significant increase in the yield of the ligand centered aminated product was observed. In absence of substrates(aryl halides), only ligand centered amination was observed. The newly formed ligands L2 and L3 obtained using primary aromatic amines as the nucleophiles were isolated from the reaction mixture and identified using X-ray crystallographic analysis. Iron complexes of the newly formed para-aminated tridentate azo-aromatic ligand, 4-N-aryl-(2-arylazo)-1,10-phenanthroline (L3b) was also used to study the C–N cross coupling reactions to check the electronic effects of the coordinated ligands on the C–N bond formation reactions (Table 1, entry 18). Several control experiments and DFT calculations were performed to understand the competitive substrate versus ligand centered amination reactions using these Fe-complexes of L1.
Table 1. Optimization of Reaction Conditionsabcd
entryFe-catalyst (mol %)solventbasetime (h)yield (%)
11a (10 mol %)tolueneKOtBu36trace
21a (10 mol %)DMFKOtBu36trace
31a (10 mol %)DioxaneKOtBu36trace
41a (10 mol %)THFKOtBu36trace
51a (10 mol %)DMSOKOtBu3668
61a (10 mol %)DMSONaH36trace
71a (10 mol %)DMSOCs2CO336trace
81a (10 mol %)DMSOK2CO336trace
91a (10 mol %)DMSOK3PO436trace
101a (10 mol %)DMSODBU3630
111a (10 mol %)DMSOKOH3635
121a (10 mol %)DMSONaOH3635
131a (10 mol %)DMSONaOtBu3667
142a (10 mol %)DMSOKOtBu3665
151b (10 mol %)DMSOKOtBu3657
162b (10 mol %)DMSOKOtBu3653
171c (10 mol %)DMSOKOtBu3668
181d(10 mol %)DMSOKOtBu3670
191a (7.0 mol %)DMSOKOtBu3656
20[1a] (8.0 mol %)DMSOKOtBu3669
21[1a] (8.0 mol %)DMSODBU3667
22[1a] (8.0 mol %)DMSONaOH3669
23[1a] (8.0 mol %)DMSOKOH3667
24L1a (10 mol %)DMSOKOtBu36 
25FeCl2 (>99.99%)DMSOKOtBu36trace
26FeCl3 (>99.99%)DMSOKOtBu36trace
27FeCl2 (>99.99%) + L (1:1)DMSOKOtBu3640
28FeCl3 (>99.99%) + L (1:1)DMSOKtBuO3640
291a + TEMPODMSOKtBuO36 
a

Stoichiometry: pyrazole (3a) (1.0 mmol; 1.0 equiv) and iodobenzene (4a) (1.2 mmol; 1.2 equiv).

b

Under argon atmosphere.

c

Base: 2.0 equiv.

d

Isolated yields after column chromatography.

Scheme 3

Scheme 3. Competitive C–N Bond Formation Reactions

Figure 1

Figure 1. ORTEP representation of L2c with ellipsoids drawn at the 50% probability level. Hydrogen atoms are omitted for clarity (N3–N4: 1.256(3) Å).

Figure 2

Figure 2. ORTEP representation of L3c with ellipsoids drawn at the 50% probability level. Hydrogen atoms are omitted for clarity (N3–N4: 1.262(4) Å).

Results and Discussion

ARTICLE SECTIONS
Jump To

Synthesis and Characterization of Catalysts

The penta-coordinated Fe(II)-catalysts, [FeII(L1a,b)Cl2] (1a, 1b), were synthesized following a reported literature method using >99.99% FeCl2 obtained from Sigma-Aldrich.(14a) [FeIIL1cCl2] (1c) was synthesized by stirring dichloromethane solution of the ligand (L1c) in the presence of excess FeCl2 (see Experimental Section for details) (Scheme 2).
The Fe(III)-complexes [FeIII(L1a,b)Cl2] (2a, 2b) were synthesized via the reaction of >99.99% pure FeCl3 and L1a,b in refluxing ethanol. New red colored air stable neutral complexes [Fe(L1a,b)Cl3] (2a, 2b) were obtained in nearly 85% yield (Scheme 2). Elemental analyses of 1c, 2a, and 2b convincingly support their formulations. The identity as well as the electronic structure formulation of 2b was also affirmed by X-ray single crystal analysis followed by SQUID magnetometry and Mössbauer spectroscopic analysis (see Supporting Information for details). It is worth mentioning here that complexes 2a and 2b upon reduction transform to complexes 1a and 1b, respectively.

Catalytic C–N Coupling Reactions

In our recent work, we showed that in the presence of 1.0 equiv of KOtBu, the complex [FeII(L1b)Cl2] (1b) undergoes one electron reduction to produce the monoanionic complex [FeII{(L1b)•–}Cl2] ([1b]) in 63% yield in 5 h and at 75 °C, 72% conversion of 1b to [1b] was observed in toluene within 3 h.(14a) Therefore, to begin with, we used the penta-coordinated complexes [FeII(L1a-c)Cl2] (1ac) to study the C–N cross coupling reactions between aryl halides and aromatic N-nucleophiles in the presence of KOtBu as the base. Our intention was to generate the one electron reduced species [FeII{(L1a-c)•–}Cl2]([1a-c]) in situ via the KOtBu mediated reduction of 1ac as reported earlier.(14a)
The reaction of 1H-pyrazole (3a) and iodobenzene (4a) was studied under various reaction conditions to find out the optimal conditions and to explore the solvent and ligand effects on the possibility of catalytic C–N bond formation reactions catalyzed by 1a. The reaction proceeded most efficiently in DMSO at 120 °C using 10 mol % of the catalyst in the presence of 2.0 equiv of KOtBu. Lowering the temperature of the reaction led to a significant decrease in yield. Among the different bases examined, the bases like NaOMe, NaOH, K2CO3, K3PO4, Cs2CO3, and DBU, which are known to be nonreducing, were found to be either less effective or ineffective to bring about the desired C–N cross-coupling reactions. The desired C–N coupled products were obtained in high yield with bases like NaOtBu or KOtBu. No desired C–N coupled product was obtained in absence of a base. Our repeated attempts on lowering the catalyst loading below 10 mol % decreased the yield significantly. On the other hand, increasing the catalyst loading to 20 mol % did not improve the yield of the C–N coupled product.
[FeIIIL1aCl3] (2a), having iron in the +3 oxidation state, also showed a similar type of activity. However, because of the higher price of >99.99% FeCl3 compared to that of >99.99% FeCl2, it was not used for further studies. Interestingly, the Fe-catalysts [FeIIL1bCl2] (1b) and [FeIIIL1bCl3] (2b) bearing Cl group at the para-position of the phenyl ring of the coordinated ligand were found to be less effective in the catalytic C–N cross coupling reactions. On the other hand, introduction of an electron donating ethyl group at the para-position of the phenyl ring of the coordinated azo-aromatic ligand does not improve the yield significantly (Table 1, entry 17). Reactions were also performed with the newly synthesized iron-complex, [FeL3bCl2] (1d) containing the para-aminated ligand 4-N-(p-anisyl)-(2-phenylazo)-1,10-phenanthroline (L3b). To our delight, this complex was also found to be effective in bringing about the desired C–N cross coupling reactions. Slightly higher yields were obtained with the Fe-complexes of 4-N-aryl-(2-arylazo)-1,10-phenanthroline ligands having electron donating -OMe substituent (Table 1, entry 18). However, because of low yield of L1c and L3b, further studies were performed using [FeL1aCl2] (1a).
To check the role of complex [1] (formed in situ via KOtBu mediated reduction) during catalytic C–N coupling reactions, we repeated the coupling of 1H-pyrazole (3a) and iodobenzene (4a) under the optimized conditions, using the preformed [1a] as the catalyst. As reported earlier during catalytic dehydrogenation of alcohols,(14a) the catalytic C–N coupling reaction also proceed efficiently using [1a] as the catalyst, affording the desired 1-phenyl-1H-pyrazole (5aa) in 69% yield (Table 1, entry 20). Almost comparable yield of the desired C–N coupled products were obtained with slightly lower catalyst loading. Reactions were also found to proceed with bases such as NaOH, KOH, DBU, which were otherwise found to be less effective when used with the unreduced complex 1a as the catalyst (Table 1, entries 20–23).
Therefore, all further catalytic reactions were studied using [FeIIL1aCl2] (1a) (10 mol %) as the catalyst, DMSO as the solvent, and KOtBu as the base. It is important to mention here that DMSO in combination with potassium tertiary butoxide produces dimsyl radical, which may also take part in the catalytic reactions. To check such possibilities, the catalytic reactions were performed in neat conditions (in absence of DMSO as the solvent) with some of the nucleophiles, which are liquid at room temperature or melts at 130 °C. The reaction was found to proceed smoothly even in absence of any added solvent like DMSO; however, the desired products were obtained in slightly lower yields.
To explore the versatility and the substrate scope of these well-defined Fe-catalysts, a variety of aryl halides (iodo, bromo, chloro) were used to study the catalytic C–N cross coupling reactions under the optimized reaction conditions using 1H-pyrazole (3a) as the nucleophilic counterpart. The desired C–N coupled products were obtained in almost comparable yields using either 1a (10 mol %) and 2.0 equiv. KOtBu or the monoanionic species [1a] (8.0 mol %) in combination with NaOH or DBU (1.5 equiv) as the base. The results are summarized in Table 2.
Table 2. N-Arylation of 1H-Pyrazole with Various Substituted Aryl Halidesabcdef
a

Stoichiometry: nucleophile (3a) (1.0 mmol; 1.0 equiv) and iodobenzene (4a-j) (1.2 mmol; 1.2 equiv).

b

2.0 equiv of KOtBu.

c

10 mol % catalyst.

d

Under argon atmosphere.

e

Isolated yields after column chromatography.

f

Yields in the parentheses were obtained when preformed [1a] was used as the catalyst and NaOH as base.

Since aryl iodides are more reactive than aryl bromides, a higher yield of the N–arylated product was obtained using iodobenzene compared to bromobenzene. Using aryl chlorides, only a trace amount of the N-arylated product was isolated. Aryl iodides containing electron donating as well as electron withdrawing functionalities proved to be effective in the catalytic C–N cross coupling reaction with 1H-pyrazole. The desired N-arylated products were obtained in higher yields starting from aryl iodides bearing electron donating groups at the ortho- or para-positions. For example, reaction of 1H-pyrazole with 4-iodoanisole produced the corresponding N-arylated product in 71% isolated yield (Table 2, entry 5).
Electron-donating groups occupying the meta-position of the aryl iodides do not seem to have any effect on the catalytic turnover. Aryl iodides having electron-withdrawing groups were also found to be compatible, although the corresponding N-arylated products were obtained in moderate to low yield (Table 2, entries 8, 9). Reaction with 1-iodonaphthalene as the electrophilic counterpart also produced the corresponding N-arylated product in moderate yield (Table 2, entry 10). The C–N cross-coupling protocol was also found to proceed with heterocyclic iodides, albeit producing the corresponding N-arylated products in lower yield (Table 2, entry 11). The poor yields obtained when using the heterocyclic iodides may be attributed to their coordinating ability, blocking the Fe-center of the catalyst. This methodology was found to be selective, as the reaction of 2-iodo phenol with 1H-pyrazole produced the corresponding N-arylated product, and no C–O bond formation was observed (Table 2, entry 12).
To further expand the substrate scope, several reactions employing a diverse range of N-nucleophiles including 1H-imidazole, 1H-indole, benzimidazole, triazole, morpholine, pyrrole, benzamide, etc. were carried out under the optimized reaction conditions with iodobenzene using 1a as the catalyst and KOtBu as the base. With all these nucleophiles, the corresponding N-arylated products were isolated in moderate to good yields. For example, 1H-imidazole, when reacted with iodobenzene under the optimized reaction conditions, produced 1-phenyl-1H-imidazole (5ba) in 72% isolated yield (Table 3, entry 2). Reaction of 1H-indole with iodobenzene under the optimized reaction conditions afforded 1-phenyl-1H-indole (5ca) in 60% isolated yield (Table 3, entry 3). 1-Phenyl-1H-benzo[d]imidazole (5da) was obtained in 61% isolated yield form the reaction of 1H-benzo[d]imidazole and iodobenzene under the optimized reaction conditions (Table 3, entry 4). Reactions of iodobenzene with piperidine, pyrrolidine, and morpholine produced the desired C–N coupled products in 69, 73, and 72% isolated yields, respectively (Table 3, entries 7–9). Triazoles were also found to be effective; however, the yields of the desired C–N coupled products are comparatively low (Table 3, entries 10, 11). Amides were also found to be compatible, the reaction of benzamide with iodobenzene also afforded the corresponding N-phenylbenzamide in 42% isolated yield (Table 3, entry 12), whereas the cyclic amide derivative (pyrrolidin-2-one) produced the corresponding N-arylated product in 50% yield (Table 3, entry 13).
Table 3. N-Arylation of Nitrogen Nucleophiles with Iodobenzene Catalyzed by [Fe(L1a)Cl2] (1a)abcde
a

Stoichiometry: nucleophile (3a-o) (1.0 mmol; 1.0 equiv) and iodobenzene (4a) (1.2 mmol; 1.2 equiv).

b

2.0 equiv of KOtBu.

c

10 mol % catalyst.

d

Under argon atmosphere.

e

Isolated yields after column chromatography.

Primary amines were also found to be effective for the C–N cross coupling reactions, catalyzed by 1a. Reaction of aniline with iodobenzene produced diphenylamine (5na) in 50% isolated yield (Table 3, entry 14). N-Arylation of iodobenzene was even achieved with cyclohexylamine; N-cyclohexylaniline (5oa) was obtained in 45% isolated yield (Table 3, entry 14). It is worthy to mention that while varying different nucleophiles, we tried to understand the reactivity pattern, whether it follows any order depending on the pKa of the attached proton. However, experimental results obtained in our case as well as with other already reported copper catalyzed reactions do not show such type of straightforward correlation with the pKa of the attached proton and hence it seems to be a overall combined effect.(6,7)
It is noteworthy to mention here that, during chromatographic purification of the reaction mixtures of iodobenzene and aniline as the nucleophile, we first observed a blue colored complex in the column. Our attempts to isolate the blue colored complex from the catalytic reaction mixture was not successful. Even after scaling up the catalytic reaction and increasing the catalyst loading to 25 mol %, we could not manage to isolate the blue colored complex from the catalytic reaction mixture. Literature survey showed that similar blue-colored complex formation was observed by Goswami and co-workers when they reacted transition-complexes of 2-arylazopyridine ligands with primary aromatic amines.(15,16) In their study, they reported metal mediated C–N bond formation at the ortho- and para-positions of the coordinated 2-arylazopyridine ligands and the observed blue color was proposed to originate from the uncoordinated -NHPh to π* (azo) transition.
To check the possibility of such type of C–N bond formation at the phenyl ring of the coordinated 2-(phenylazo)-1,10-phenanthroline ligand (L1a), demetalation reaction was carried out to isolate the pure organic ligand (Scheme 3). In a typical reaction, the ethanol solution of the blue colored complex was stirred overnight in the presence of excess ammonium hydroxide, which leads to demetalation and formation of iron hydroxide salts. After filtration of this reaction mixture and usual workup, the organic part was purified by column chromatography, which indeed allowed us to isolate two new red colored organic ligands L2a and L3a, respectively, of same molecular mass of 376 amu having an extra PhNH-moiety attached to the parent ligand L1a. The simulated isotropic distribution of these two mass spectra matches well with the given same formula (see Supporting Information). To check the generality of these ligand centered amination reactions, 4-methoxy aniline and 4-chloro aniline were used as the nucleophiles, and after similar demetalation we successfully isolated L2b,c and L3b,c from the reaction mixtures. 1H NMR spectra of L2a and L3a indeed confirm the formation of two new organic ligands containing an additional −NHPh arm when compared to parent ligand L1a (see Supporting Information). Further characterization by single crystal X-ray diffraction certainly approves the formation of C–N bond at the ortho- and para-positions of L1a (see further).
X-ray quality single crystals of the ligand L2c were grown via slow evaporation of its dichloromethane/hexane (10:1) solution. An ORTEP representation of L2c is displayed in Figure 1. Formation of a new tetradentate scaffold 2-[(2-N-phenylamino)phenylazo]-1,10-phenanthroline (L2c) via the construction of a new C–N bond at the ortho-position of the parent azo-aromatic ligand L1a is indeed confirmed from the single crystal structure of L2c. The N=N distance was found to be 1.256(3) Å.
Similarly, single crystals of the ligand L3c were grown via slow evaporation of its dichloromethane/hexane (10:1) solution. ORTEP representation of L3c is shown in Figure 2. The formation of a new C–N bond at the para- position of the azo-aromatic ligand L1a affording a new tridentate azo-aromatic ligand 2-[(4-N-phenylamino)phenylazo]-1,10-phenanthroline (L3c) is indeed confirmed from the X-ray structure. The N=N distance was found to be 1.262(4) Å.
These results using primary aromatic amines as the nucleophiles indeed show competitive substrate(iodobenzene) versus ligand centered C–N bond formation reactions. Control reactions in absence of substrate (iodobenzene) only showed ligand centered amination reaction (Scheme 3). However, in absence of metal ion, when the free ligands were subjected for C–N cross-coupling reaction under the optimized reaction conditions, no ligand centered amination was observed. It is worthy to mention here that in similar complexes ortho- C–N bond formation is observed only when there is some vacant coordination site or labile ligands are available at the metal center. For stable, coordinatively saturated and kinetically inert transition metal complexes where there is no such vacant coordination site available, only para-amination reactions were observed.(16) Therefore, The C–N bond formation reaction at the ortho-position of the coordinated ligand L1 is believed to proceed via an inner sphere mechanism where the coordination of the nucleophile to the iron-center is one of the steps for the reaction to proceed. On the other hand, the C–N bond formation at the para-position of the coordinated ligand L1 is believed to be an outer-sphere nucleophilic substitution. In line with our arguments, in absence of the competitor substrate(iodobenzene), the ligand centered C–N bond formation both at the ortho- and para-positions was found to increase substantially (Scheme 4).

Scheme 4

Scheme 4. Ligand Centered C–N Coupling in Absence of Substrate (Iodobenzene)

Neat conditions.

Ligand centered amination using primary aromatic amine and isolation of two new series of azo-aromatic ligands L2a-c and L3a-c prompted us to recheck the reaction mixtures of various nitrogen nucleophiles and iodobenzene. ESI-MS spectra of the catalytic C–N coupling reactions between 1H-pyrazole with iodobenzene also point to a competitive substrate(aryl halides) versus ligand centered amination reactions (see Supporting Information).

Control Experiments and DFT Studies To Obtain Mechanistic Insight into Observed Competitive Substrate versus Ligand Centered C–N Coupling

To understand the mechanism, some control experiments were carried out. In absence of the catalyst [FeL1aCl2] (1a), no desired C–N coupled product was obtained. Using >99.99% FeCl2 or >99.99% FeCl3, obtained from Aldrich, only a trace amount of the N-arylated product was obtained as reported earlier by Buchwald and Bolm.(6i) The lower reactivity may be attributed to the thermodynamically unfavorable metal centered redox events associated with the different elementary steps of the C–N cross coupling reactions; however, the exact reason of low reactivity of pure iron salts is not completely understood. Moreover, instead of using the preformed catalyst [FeL1aCl2] (1a), when a 1:1 mixture of >99.99% FeCl2 or >99.99% FeCl3 (obtained from Aldrich) and L1a was used, a significant decrease of product yield was observed (Table 1, entry 27, 28). To rule out the possibility of contaminants,(6i−l) all the catalytic reactions were performed using properly washed single crystals of the iron complex. To check the possibility of any copper or palladium contamination present in our catalyst samples, inductively coupled plasma mass spectrometry (ICPMS) experiments were carried out. Presence of only 37 ppb of copper and 02 ppb of palladium impurities have been detected, which are far below the level (5.0 ppm) of copper impurities known to produce 97% of C–N coupled product in the presence of DMEDA ligand.(6i) To check other possible sources of copper and palladium, KOtBu and DMSO have also been analyzed using ICPMS. However, no copper or palladium impurities have been detected. Next to be more sure about the possibility of contaminations in/on the glassware that we used during the catalytic reactions, 1H-pyrazole and iodobenzene were refluxed in DMSO at 130 °C in randomly selected Schlenk tubes available in our laboratory. Four different Schlenk tubes were used for these control reactions and in all the cases no C–N coupled product was obtained. As a further control experiment, the cross-coupling of 1H-pyrazole (3a) and iodobenzene (4a) was carried out under optimized reaction conditions using a similar copper(II) complex, CuL1Cl2, synthesized via the reaction of L1 with CuCl2 under the similar reaction conditions reported for [FeL1Cl2].(14a) After repeated experiments using CuL1Cl2 (1.0 ppm) as catalyst, we obtained only 7–10% of the desired C–N coupled product. The results obtained from these above experiments confirm the definite involvement of our catalyst, [FeL1aCl2] (1a), in the catalytic turnover.
The coordinated ligand is redox noninnocent and undergoes reduction to produce an azo-anion radical. Therefore, to probe the formation of any organic radical as well as to confirm the participation of the coordinated ligand during catalysis, a radical scavenger was used while carrying out the catalytic reactions. In presence of one equivalent of TEMPO, the catalytic reaction was totally shut down. It is noteworthy to mention here that, in the presence of excess KOtBu, the complexes [Fe(L1a/b)Cl2] (1a/b) undergo one-electron reduction producing azo-anion radical complexes [FeII{(La/b)•–}Cl2] ([1a/b]), which then act as the actual catalyst in C–N coupling reactions as was reported previously during catalytic dehydrogenation of benzylic alcohols.(14a) Indeed, the prereduced catalyst [1a] showed almost similar type of efficiency during C–N cross-coupling reactions as was observed during optimizations (see Table 1 and 2).
On the basis of available literature and the conclusions drawn from various control experiments mentioned above, a plausible mechanism is outlined in Scheme 5. The reaction is believed to begin with the KOtBu-mediated reduction of 1 to form the active catalyst azo-anion radical complex A ([1]), which then undergoes oxidative addition with iodobenzene to produce the intermediate B. This two-electron step is believed to involve concerted one-electron oxidation of both the metal and the ligand radical, to produce intermediate B. In the next step, the deprotonated nucleophile binds the Fe-center to form the intermediate C. Finally, intermediate (C) undergoes reductive elimination to release the desired product.

Scheme 5

Scheme 5. Proposed Mechanism
DFT calculations were performed to further explore the mechanism of the present iron-catalyzed C–N cross coupling reactions (for details, see Experimental Section and Supporting Information). Plausible low-barrier C–N coupling pathways were investigated at the BP86 and def2-TZVP level using [1a] as the catalyst (Scheme 6). Activation of the Ar–I bond is the first step in the computed catalytic cycle. Neutral complex B′ is formed upon displacement of Cl in anionic complex A. It is difficult to calculate thermodynamic energy differences for displacement reactions where the charge is not constant. Under the reaction conditions, however, such transformations are easily accessible. Cleavage of the Ar–I bond in B′ leads to formation of B via TS-1 with a barrier of +16.7 kcal mol–1. We also considered coordination of Ar in a different fashion with the aryl group directed away from the 2-(arylazo)-1,10-phenanthroline ligand. This pathway proceeds with a relatively higher barrier of +21.2 kcal mol –1 and leads to B1, which is an isomer of B with the aryl group in the equatorial plane (more details in the Supporting Information).

Scheme 6

Scheme 6. Computed Pathway for Substrate Activation by Cleavage of Aryl–Iodide Bond in Ar–I
The next step is the displacement of the iodide ligand in B by a deprotonated pyrazole moiety, which leads to the formation of complex C. In complex C, the noncoordinated N in pyrazole makes a nucleophilic attack on the aryl moiety leading to formation of Ar-Nu adduct D′ (Scheme 7). The computed barrier for this step is +16.6 kcal mol–1.(17) Other possible pathways for Ar–Nu coupling involving (i) direct nucleophilic attack of another pyrazole N, which is coordinated to Fe, and (ii) Ar–Nu coupling with Ar in axial position were found to proceed with higher barriers (see Supporting Information).(18)

Scheme 7

Scheme 7. Computed Pathway for Ar–Nu Coupling after Ar–I Bond Activation
The noncoordinated N in pyrazole in complex C can also attack the ortho-carbon of the phenyl group of the coordinated ligand, leading to formation of complex C′ via TSC–C’ over a TS barrier of +15.0 kcal mol–1. Formation of complex C′ is an endergonic process and it can easily convert back to complex C via the backward reaction over a TS barrier of +8.9 kcal mol–1. It is therefore expected that complexes C and C′ are in equilibrium with each other, in agreement with experimental observations (vide supra).
Finally, the direct release of the product from D′ to form D was found to be unfavorable (endergonic by ∼20 kcal mol–1). Instead of a direct release, a Cl ligand could add on D′ to form ANu-Ar. The release of Ar–Nu from ANu-Ar to regenerate catalysts A was computed to be downhill by 5.3 kcal mol–1 with a very small transition state barrier of +1.4 kcal mol–1 with respect to the Ar-Nu adduct AAr-Nu (Scheme 8).

Scheme 8

Scheme 8. Release of Ar–Nu and Catalyst Regeneration

Conclusions

ARTICLE SECTIONS
Jump To

In summary, we have reported an alternative approach of iron catalyzed carbon–nitrogen cross coupling reactions of a wide range of nucleophiles and aryl halides using well-defined iron-complexes featuring redox noninnocent 2-(arylazo)-1,10-phenanthroline ligands. In addition to substrate centered C–N coupling, competing C–N coupling reactions were also observed at the ortho- and para-positions of the phenyl ring of the coordinated azo-aromatic ligands affording new tetradentate ligands, 2-N-aryl-(2-arylazo)-1,10-phenanthroline (L2) and tridentate ligands, 4-N-aryl-(2-arylazo)-1,10-phenanthroline (L3), respectively. Mechanistic studies reveal that the active catalyst is the one electron reduced species [1], and both metal and the coordinated ligand participate in a cooperative manner during electron transfer processes involved in the elementary steps of the catalytic reaction. Experimental and DFT studies were carried out to understand the competitive substrate versus ligand centered amination reactions. Overall, these results reveal a new window where azo-aromatic ligands in combination with other metal ions can be used to explore various catalytic reactions.

Experimental Section

ARTICLE SECTIONS
Jump To

Materials

The >99.99% FeCl2, > 99.99% FeCl3, and iodobenzenes were obtained from Sigma-Aldrich. L1a-c and [FeIIL1a-cCl2] (1ac) were synthesized following the reported literature methods using >99.99% FeCl2 obtained from Sigma-Aldrich as the iron source.(14) All other starting materials, chemicals, and reagents were obtained from the available commercial sources and used as received.

Physical Measurements

Bruker Avance 300/400/500 MHz and JEOL 400 MHz spectrometers were used for recording 1H NMR spectra. TMS was used as the internal standard. Micro mass Q-TOF mass spectrometer (serial no. YA 263) was used for recording ESI mass spectra. Room temperature magnetic moment measurements for 2b were carried out with Gouy balance (Sherwood Scientific, Cambridge, U.K.). The Mössbauer spectrum of 2b was recorded with a 57Co source in a Rh matrix using an alternating constant acceleration Wissel Mössbauer spectrometer operated in the transmission mode and equipped with a Janis closed-cycle helium cryostat. Isomer shifts are given relative to iron metal at ambient temperature. Using Quantum-Design MPMS-XL-5 SQUID magnetometer equipped with a 5 T magnet, variable temperature magnetic moment measurement for 2b was performed in the temperature range from 295 to 2.0 K at 0.5 T magnetic field. The powdered sample was contained in a gel bucket and fixed in a nonmagnetic sample holder. Each raw data file for the measured magnetic moment was corrected for the diamagnetic contribution of the sample holder and the gel bucket. The molar susceptibility data were corrected for the diamagnetic contribution. An inductively coupled plasma orthogonal acceleration time-of-flight mass spectrometer (ICP-oa-TOF-MS), model: 8000R (GBC, Australia), was used for the determination of copper and palladium impurities. ICPOES (model ULTIMA 2 (Jobin Yvon—Horiba, France) was used to quantify the amount of iron present in the catalyst.

Synthesis

Synthesis of L1c

L1c was prepared following the literature procedure(14a) using 2-amino-1,10-phenanthroline and 4-ethylnitrosobenzene as the coupling partners. Yield: 30%. Anal. calcd: C, 76.90; H, 5.16; N, 17.94; found: C, 76.98; H, 5.30; N, 17.87. UV–vis: λmax/nm (ε, M–1 cm–1), 236 (32,229), 275 (23,501), 350 (25,600). IR (KBr, cm–1): 1701 (ν, C=N), 1418 (ν, N=N). ESI-MS: m/z 313.14 [L1c + H]+. 1H NMR (500 MHz, CDCl3): δ 9.13 (s, 1H), 8.184–8.209 (m, 1H), 8.092–8.077 (t, J = 4 Hz, 1H), 8.03 (d, J = 8 Hz, 2H), 7.99–7.93 (m, 1H), 7.63 (d, 2H), 7.51–7.49 (m, 1H), 7.29 (d, J = 8 Hz, 2H), 2.67–2.62 (m, 2H), 1.19 (t, J = 6 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ162.1, 150.9, 150.5, 149.4, 146.3, 145.6, 138.4, 136.0, 129.4, 129.0, 128.6, 127.5, 126.0, 124.1, 123.2, 113.4, 28.9, 15.2.

Synthesis of [FeL1aCl2] (1a) and [FeL1bCl2] (1b)

Complexes 1a and 1b were synthesized following the literature procedure.(14a)

Synthesis of [FeL1cCl2] (1c)

One-hundred milligrams (0.320 mmol) of ligand Lc was dissolved in 20 mL of dichloromethane and was taken in a dropping funnel and was added dropwise to a suspension of FeCl2 (127 mg (1.0 mmol)) in dichloromethane in a 100 mL round-bottom flask fitted with a stir bar. The dropwise addition of Lc was continued over 20 min. During this time, the color of the solution in the round-bottom flask changed from light yellow to dark brown. After the addition was complete, the whole solution was stirred for additional 30 min. The solution was then passed through a cotton filter, and the filtrate, thus obtained, was dried under vacuum to obtain a solid residue. Fractional crystallization of the solid residue in dichloromethane/hexane solvent mixture afforded the pure complex 1c. Yield: 90%. Anal. calcd: C, 54.70; H, 3.67; N, 12.76; found: C, 54.60; H, 3.77; N, 12.67. ESI-MS [M – Cl]+: m/z 402.98. UV–vis: λmax/nm (ε, M–1 cm–1), 239 (17,929), 266 (12,718), 355 (16,829). IR (KBr, cm–1): 1744 (ν, C=N), 1438(ν, N=N).

Synthesis of [FeL3bCl2] (1d)

Fifty milligrams (0.123 mmol) of ligand L3b was dissolved in 15 mL of dichloromethane and taken in a dropping funnel and was added dropwise to a suspension of FeCl2 (24.5 mg, 0.193 mmol) in dichloromethane in a 100 mL round-bottom flask fitted with a stir bar. The dropwise addition of L3b was continued for 20 min. During this time, the color of the solution in the round-bottom flask changed from light yellow to dark blue. The whole solution was stirred for additional 30 min and filtered. The filtrate was then evaporated to dryness and fractional crystallization of the solid residue in dichloromethane/hexane solvent mixture yielded the pure complex 1d. Yield: 80%. Anal. calcd: C, 56.42; H, 3.60; N, 13.16; found: C, 56.32; H, 3.72; N, 13.06. UV–vis: λmax/nm (ε, M–1 cm–1), 235 (12,609), 292 (9,057), 358 (4,783), 563 (b,555), 767 (b, 1231). IR (KBr, cm–1)): 1724 (ν, C=N), 1431(ν, N=N).

Synthesis of [FeL1aCl3] (2a)

In ethanol, 50 mg (0.17 mmol) of the ligand (L1a) was allowed to dissolve, and then 27.5 mg (0.17 mmol) of FeCl3 was poured to it. Upon addition of FeCl3, the orange color of the solution instantaneously changed to red, and a dark red colored precipitate appeared after few minutes. The mixture was refluxed for four hours, and the precipitate was then filtered off. The complex was purified by fractional crystallization from dichloromethane/hexane solvent mixtures. Yield: 90%. Anal. calcd: C, 48.42; H, 2.71; N, 12.55; found: C, 48.47; H, 2.80; N, 12.48. UV–vis: λmax/nm (ε, M–1 cm–1), 231 (16,072), 337 (7,308), 400 (9598). IR (KBr, cm–1): 1705 (ν, C=N), 1450 (ν, N=N).

Synthesis of [FeL1bCl3] (2b)

The complex 2b was synthesized following the same procedure described for the synthesis of complex 2a. Yield: 91%. Anal. calcd: C, 44.95; H, 2.31; N, 11.65; found: C, 44.89; H, 2.40; N, 11.73. UV–vis: λmax/nm (ε, M–1 cm–1), 245 (17,322), 403 (10,231). IR (KBr, cm–1): 1715 (ν, C=N), 1493 (ν, N=N). SQUID Magnetometry: (300–50 K) χMT = 4.37 cm3 mol–1 K. Mossbauer Spectroscopy: δ = 0.48 mm s–1, ΔEQ = 1.25 mm s–1.

General Procedure for Catalytic C–N Bond Formation

In a 50 mL oven-dried Schlenk tube, 1.0 mmol nucleophile, 10.0 mol % catalyst, and 2.0 equiv KOtBu were added. The tube was capped with a rubber septum. It was then evacuated and argon was backfilled. The same procedure was repeated three times. To this mixture, 1.2 mmol aryl halide, 4.0 mL of dry and degassed DMSO was added using a syringe. All joints were sealed with Teflon tape. The tube was then placed in an oil bath preheated at 120 °C. The reaction was continued for 36 h. Once the reaction was complete, the reaction mixture was cooled to room temperature. The reaction mixture was poured into saturated brine solution (approximately 100 mL). It was then extracted three times with dichloromethane. The combined organic portion was evaporated and subjected to column chromatography using petroleum ether/ethyl acetate as the eluent.

Demetalation and Isolation of L2 and L3 from the Catalytic Reaction Mixture

The blue portion, obtained from the reaction mixture during column chromatography, was dissolved in EtOH, and excess NH4OH was then added to it. Upon addition of NH4OH, the color of the solution immediately changed from blue to red. The resulting solution was stirred overnight at room temperature. The ethanol was evaporated, and the residue was dissolved in dichloromethane and purified by preparative TLC using ethyl acetate/petroleum ether as the eluent.

Reaction of Complex 1a with Primary Amines in Neat Condition

A 50 mL round-bottom flask was charged with 1.0 mmol of complex 1a, 2.0 equiv KOtBu, and excess of aniline (or substituted anilines). The flask was then placed in a water bath and heated for 30 min. During this period, the color of the reaction mixture gradually changed to blue. The excess aniline was removed by repeated washing with hot hexane solution. The blue semisolid compound was then dissolved in EtOH, and excess of NH4OH was added to it. The solution was stirred overnight. During this period, a black precipitate was formed. The red colored solution, thus obtained, was filtered and dried in vacuum. The residue was purified by preparative TLC to isolate L2a-c and L3a-c (see Supporting Information for details).

ICPMS and ICPOES Experiments

A 0.0108 g of sample was slowly heated to dryness with 5.0 mL of concentrated nitric acid in a hot plate. This step was repeated twice. After cooling, 2.0% nitric acid was again added into the samples, and the whole content was transferred into a 50 mL volumetric flask with repeated washing of the digestion vessel, and volume was made up with same nitric acid. This 50 mL yellow colored solution was used for estimation of Pd and Cu using ICPMS.

X-ray Crystallography

Suitable X-ray-quality crystals of 2b, L2c, and L3c were grown via slow evaporation of their dichloromethane–hexane (10:1) solutions. The X-ray data of 2b, L2c, and L3c were collected on a Bruker SMART Apex II diffractometer equipped with a CCD area detector, with monochromated Mo Kα radiation (λ = 0.71073 Å). 2b: Out of the total 29134 reflections collected, 5066 unique (Rint = 0.024) reflections satisfying the (I > 2σ(I)) criterion were used for the final X-ray structure analysis. L2c: Out of the total 46 137 reflections collected, 7405 unique (Rint = 0.127) reflections satisfying the (I > 2σ(I)) criterion were used for the final X-ray structure analysis. In the single-crystal structure of L2c, the hydrogen atoms bonded to O200 of water solvent molecule were not discernible from the last final difference Fourier map, and consequently their positions were not considered. L3c: Out of the total 30 924 reflections collected, 7160 unique (Rint = 0.216) reflections satisfying the (I > 2σ(I)) criterion were used for the final X-ray structure analysis.
SAINT-NT software package was used for data reduction.(19) Using SADABS program, multiscan absorption correction was applied to all intensity data.(20) Combination of direct methods followed by difference Fourier syntheses were used to solve the structures. Full-matrix least-squares refinement was done on F2 using the SHELX-2013 program.(21) Anisotropic thermal displacements were employed during refinement of all non-hydrogen atoms. The details of the X-ray crystal structures along with the refinement details are summarized in Table S1.

Computational Details

All DFT geometry optimizations were performed with the Turbomole program(22) coupled to the PQS Baker optimizer(23) via the BOpt package.(24) Geometries were fully optimized as minima or transition states using the BP86 functional(25) and the resolution-of-identity (ri) method(26) using the Turbomole def2-TZVP basis(27) for all atoms. Grimme’s dispersion corrections (D3 version, implemented with the keyword disp3 in Turbomole) were applied in all geometry optimizations.(28) All minima (no imaginary frequencies) and transition states (one imaginary frequency) were characterized by calculating the Hessian matrix. ZPE and gas-phase thermal corrections (entropy and enthalpy, 298 K, 1 bar) from these analyses were calculated. The relative (free) energies obtained from these calculations are reported in the main text of this paper. Intrinsic reaction coordinate (IRC) calculations were performed to confirm the nature of the transition states.
By calculation of the partition function of the molecules in the gas phase, the entropy of dissociation or coordination for reactions in solution was overestimated (overestimated translational entropy terms in the gas phase compared to solutions). For reactions in solution, we therefore corrected the Gibbs free energies for all steps involving a change in the number of solute species. The applied correction term is a correction for the condensed phase (CP) reference volume (1 L mol–1) compared to the gas phase (GP) reference volume (24.5 L mol–1). This leads to an entropy correction term (SCP = SGP + R ln{1/24.5}) for all species, which, combined with neglecting the RT term, corrects the relative free energies (298 K) of all associative (−2.5 kcal mol–1) and dissociative steps (+2.5 kcal mol–1).(29)

Supporting Information

ARTICLE SECTIONS
Jump To

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b02877.

  • ESI-MS spectra, 1H NMR spectra, ORTEP, Cartesian coordinates of optimized structures (PDF)

Accession Codes

CCDC 18478281847830 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by e-mailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

#Author Contributions

S.S. and R.S. contributed equally to this work.

Author Contributions

V.S. performed the computational work.

The authors declare no competing financial interest.

Author Status

U.J. died on August 31, 2018.

Dedication

Dedicated in memory of Ms. Upasona Jash.

Terms & Conditions

Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACS website may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machine-readable form or any other form without permission from the American Chemical Society. For permission to reproduce, republish and redistribute this material, requesters must process their own requests via the RightsLink permission system. Information about how to use the RightsLink permission system can be found at http://pubs.acs.org/page/copyright/permissions.html.

Acknowledgments

ARTICLE SECTIONS
Jump To

DST (Project: YSS/2015/001552) supported the present research. S.S. acknowledges IIESTS, R.S. acknowledges RGNF, U.J. acknowledges DST-Inspire, S.D. acknowledges UGC for fellowship. Financial Support from IIESTS is duly acknowledged. We sincerely thank Asish Kr. Singha Deb, Scientific Officer, BARC, Trombay, Mumbai 400 085, India, for carrying out the ICPMS and ICPOES experiments. P.B. thanks CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT ref. UID/CTM/50011/2013), financed by national funds through the FCT/MEC and when appropriate cofinanced by FEDER under the PT2020 Partnership Agreement”. V.S. and B.d.B. acknowledge support from the Research Priority Area Sustainable chemistry of the University of Amsterdam, and the Industrial Partnership Programme (IPP) Computational Sciences for Energy Research (project 13CSER003), which is financially supported by The Netherlands Organization for Scientific Research (NWO) and is cofinanced by Shell Global Solutions International B.V. The calculations were carried out on the Dutch national e-infrastructure with the support of the SURF cooperative. S.D. and F.M. thank the University of Göttingen for support. Use of the single crystal X-ray facility at SAIF-IIESTS is duly acknowledged.

References

ARTICLE SECTIONS
Jump To

This article references 29 other publications.

  1. 1
    (a) Hili, R.; Yudin, A. K. Making Carbon-nitrogen Bonds in Biological and Chemical Synthesis. Nat. Chem. Biol. 2006, 2, 284287, DOI: 10.1038/nchembio0606-284 .
    (b) Ullmann, F. Ueber eine neue bildungsweise von diphenylaminderivaten. Ber. Dtsch. Chem. Ges. 1903, 36, 23822384, DOI: 10.1002/cber.190303602174 .
    (c) Goldberg, I. Ueber Phenylirungen Bei Gegenwart von Kupfer als Katalysator. Ber. Dtsch. Chem. Ges. 1906, 39, 16911692, DOI: 10.1002/cber.19060390298 .
    (d) Barton, D. H. R.; Nakanishi, K.; Meth-Cohn, O. Comprehensive Natural Products Chemistry; Elsevier: Oxford, 1999; Vol. 4.
    (e) Ricci, A. Amino Group Chemistry, From Synthesis to the Life Sciences; Wiley-VCH: Weinheim, 2007.
    (f) Bariwal, J.; Van der Eycken, E. C–N bond forming cross-coupling reactions: an overview. Chem. Soc. Rev. 2013, 42, 92839303, DOI: 10.1039/c3cs60228a .
    (g) Shin, K.; Kim, H.; Chang, S. Transition-Metal-Catalyzed C–N Bond Forming Reactions Using Organic Azides as the Nitrogen Source: A Journey for the Mild and Versatile C–H Amination. Acc. Chem. Res. 2015, 48, 10401052, DOI: 10.1021/acs.accounts.5b00020 .
    (h) Park, Y.; Kim, Y.; Chang, S. Transition Metal-Catalyzed C–H Amination: Scope, Mechanism, and Applications. Chem. Rev. 2017, 117, 92479301, DOI: 10.1021/acs.chemrev.6b00644
  2. 2
    (a) Craig, P. N. Comprehensive Medicinal Chemistry; Drayton, C. J., Ed.; Pergamon Press: New York, 1991; Vol. 8.
    (b) Cozzi, P.; Carganico, G.; Fusar, D.; Grossoni, M.; Menichincheri, M.; Pinciroli, V.; Tonani, R.; Vaghi, F.; Salvati, P. Imidazol-1-yl and pyridin-3-yl derivatives of 4-phenyl-1,4-dihydropyridines combining Ca2+ antagonism and thromboxane A2 synthase inhibition. J. Med. Chem. 1993, 36, 29642972, DOI: 10.1021/jm00072a017 .
    (c) Katritzky, A. R.; Rees, C. W.; Scriven, E. F. V. Comprehensive Heterocyclic Chemistry II; Elsevier: Oxford, 1996.
    (d) Fairlamb, I. J. S. Regioselective (site-selective) Functionalisation of Unsaturated Halogenated Nitrogen, Oxygen and Sulfur Heterocycles by Pd-catalysed Cross-couplings and Direct Arylation Processes. Chem. Soc. Rev. 2007, 36, 10361045, DOI: 10.1039/b611177g
  3. 3
    (a) Ruiz-Castillo, P.; Buchwald, S. L. Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions. Chem. Rev. 2016, 116, 1256412649, DOI: 10.1021/acs.chemrev.6b00512 .
    (b) Ueda, S.; Su, M.; Buchwald, S. L. Completely N1-Selective Palladium-Catalyzed Arylation of Unsymmetric Imidazoles: Application to the Synthesis of Nilotinib. J. Am. Chem. Soc. 2012, 134, 700706, DOI: 10.1021/ja2102373 .
    (c) Shuler, S. A.; Yin, G.; Krause, S. B.; Vesper, C. M.; Watson, D. A. Synthesis of Secondary Unsaturated Lactams via an Aza-Heck Reaction. J. Am. Chem. Soc. 2016, 138, 1383013833, DOI: 10.1021/jacs.6b08932 .
    (d) Khatun, N.; Modi, A.; Ali, W.; Patel, B. K. Palladium-Catalyzed Synthesis of 2-Aryl-2H-Benzotriazoles from Azoarenes and TMSN3. J. Org. Chem. 2015, 80, 96629670, DOI: 10.1021/acs.joc.5b01706 .
    (e) Zhou, Y.; Verkade, J. G. Highly Efficient Ligands for the Palladium-Assisted Double N-Arylation of Primary Amines for One-Sep Construction of Carbazoles. Adv. Synth. Catal. 2010, 352, 616620, DOI: 10.1002/adsc.200900846 .
    (f) Ikawa, T.; Barder, T. E.; Biscoe, M. R.; Buchwald, S. L. Pd-Catalyzed Amidations of Aryl Chlorides Using Monodentate Biaryl Phosphine Ligands: A Kinetic, Computational, and Synthetic Investigation. J. Am. Chem. Soc. 2007, 129, 1300113007, DOI: 10.1021/ja0717414 .
    (g) Hicks, J. D.; Hyde, A. M.; Cuezva, A. M.; Buchwald, S. L. Pd-Catalyzed N-Arylation of Secondary Acyclic Amides: Catalyst Development, Scope, and Computational Study. J. Am. Chem. Soc. 2009, 131, 1672016734, DOI: 10.1021/ja9044357 .
    (h) Beletskaya, I. P.; Cheprakov, A. V. The Complementary Competitors: Palladium and Copper in C–N Cross-Coupling Reactions. Organometallics 2012, 31, 77537808, DOI: 10.1021/om300683c .
    (i) Vo, G. D.; Hartwig, J. F. Palladium-Catalyzed Coupling of Ammonia with Aryl Chlorides, Bromides, Iodides, and Sulfonates: A General Method for the Preparation of Primary Arylamines. J. Am. Chem. Soc. 2009, 131, 1104911061, DOI: 10.1021/ja903049z .
    (j) Brusoe, A. T.; Hartwig, J. F. Palladium-Catalyzed Arylation of Fluoroalkylamines. J. Am. Chem. Soc. 2015, 137, 84608468, DOI: 10.1021/jacs.5b02512 .
    (k) Green, R. A.; Hartwig, J. F. Palladium-Catalyzed Amination of Aryl Chlorides and Bromides with Ammonium Salts. Org. Lett. 2014, 16, 43884391, DOI: 10.1021/ol501739g
  4. 4
    (a) Wang, H.; Yu, Y.; Hong, X.; Tan, Q.; Xu, B. Rhodium-Catalyzed Direct ortho C–N Bond Formation of Aromatic Azo Compounds with Azides. J. Org. Chem. 2014, 79, 32793288, DOI: 10.1021/jo500412w .
    (b) Andersson, P. G.; Dauban, P.; Lescot, C.; Diaz-Requejo, M. M.; Perez, P. J. Rh-, Ag-, and Cu-Catalyzed C–N Bond Formation. Innovative Catalysis in Organic Synthesis: Oxidation, Hydrogenation, and C-X Bond Forming Reactions; Wiley, 2012. DOI: DOI: 10.1002/9783527646586.ch12 .
    (c) Song, G.; Wang, F.; Li, X. C–C, C–O and C–N bond formation via rhodium(III)-catalyzed oxidative C–H activation. Chem. Soc. Rev. 2012, 41, 36513678, DOI: 10.1039/c2cs15281a .
    (d) Tang, C.; Yuan, Y.; Cui, Y.; Jiao, N. Rh-Catalyzed Diarylamine Synthesis by Intermolecular C–H Amination of Heteroarylarenes. Eur. J. Org. Chem. 2013, 2013, 74807483, DOI: 10.1002/ejoc.201301430
  5. 5
    (a) Yi, C. S. Recent Advances in the Synthetic and Mechanistic Aspects of the Ruthenium-Catalyzed Carbon-heteroatom Bond Forming Reactions of Alkenes and Alkynes. J. Organomet. Chem. 2011, 696, 7680, DOI: 10.1016/j.jorganchem.2010.08.002 .
    (b) Ackermann, L.; Lygin, A. V.; Hofmann, N. Ruthenium-Catalyzed Oxidative Synthesis of 2-Pyridones through C–H/N–H Bond Functionalizations. Org. Lett. 2011, 13, 32783281, DOI: 10.1021/ol201244s .
    (c) Huang, L.; Arndt, M.; Gooßen, K.; Heydt, H.; Gooßen, L. Late Transition Metal-Catalyzed Hydroamination and Hydroamidation. Chem. Rev. 2015, 115, 25962697, DOI: 10.1021/cr300389u .
    (d) Arockiam, P. B.; Bruneau, C.; Dixneuf, P. H. Ruthenium(II)-Catalyzed C–H Bond Activation and Functionalization. Chem. Rev. 2012, 112, 58795918, DOI: 10.1021/cr300153j .
    (e) Utsunomiya, M.; Hartwig, J. F. Ruthenium-Catalyzed Anti-Markovnikov Hydroamination of Vinylarenes. J. Am. Chem. Soc. 2004, 126, 27022703, DOI: 10.1021/ja031542u .
    (f) Takemiya, A.; Hartwig, J. F. Rhodium-Catalyzed Intramolecular, Anti-MarkovnikovHydroamination. Synthesis of 3-Arylpiperidines. J. Am. Chem. Soc. 2006, 128, 60426043, DOI: 10.1021/ja058299e .
    (g) Wu, L.; Fleischer, I.; Jackstell, R.; Beller, M. Efficient and Regioselective Ruthenium-catalyzed Hydro-aminomethylation of Olefins. J. Am. Chem. Soc. 2013, 135, 39893996, DOI: 10.1021/ja312271c
  6. 6
    (a) Antilla, J. C.; Klapars, A.; Buchwald, S. L. The Copper-Catalyzed N-Arylation of Indoles. J. Am. Chem. Soc. 2002, 124, 1168411688, DOI: 10.1021/ja027433h .
    (b) Davis, O. A.; Hughes, M.; Bull, J. A. Copper-Catalyzed N-Arylation of 2-Imidazolines with Aryl Iodides. J. Org. Chem. 2013, 78, 34703475, DOI: 10.1021/jo400120r .
    (c) Kim, H.; Chang, S. Transition-Metal-Mediated Direct C–H Amination of Hydrocarbons with Amine Reactants: The Most Desirable but Challenging C–N Bond-Formation Approach. ACS Catal. 2016, 6, 23412351, DOI: 10.1021/acscatal.6b00293 .
    (d) Rasheed, S.; Rao, D. N.; Das, P. Copper-Catalyzed Inter- and Intramolecular C–N Bond Formation: Synthesis of Benzimidazole-Fused Heterocycles. J. Org. Chem. 2015, 80, 93219327, DOI: 10.1021/acs.joc.5b01396 .
    (e) Stabile, P.; Lamonica, A.; Ribecai, A.; Castoldi, D.; Guercio, G.; Curcuruto, O. Mild, convenient and versatile Cu-mediated synthesis of N-aryl-2-imidazolidinones. Tetrahedron Lett. 2010, 51, 32323235, DOI: 10.1016/j.tetlet.2010.04.064 .
    (f) Hartwig, J. F. Evolution of a Fourth Generation Catalyst for the Amination and Thioetherification of Aryl Halides. Acc. Chem. Res. 2008, 41, 15341544, DOI: 10.1021/ar800098p .
    (g) Strieter, E. R.; Bhayana, B.; Buchwald, S. L. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides. J. Am. Chem. Soc. 2009, 131, 7888, DOI: 10.1021/ja0781893 .
    (h) Zhu, L.; Cheng, L.; Zhang, Y.; Xie, R.; You, J. Highly Efficient Copper-Catalyzed N-Arylation of Nitrogen-Containing Heterocycles with Aryl and Heteroaryl Halides. J. Org. Chem. 2007, 72, 27372743, DOI: 10.1021/jo062059f .
    (i) Buchwald, S. L.; Bolm, C. On the Role of Metal Contaminants in Catalyses with FeCl3. Angew. Chem., Int. Ed. 2009, 48, 55865587, DOI: 10.1002/anie.200902237 .
    (j) Larsson, P.-F.; Correa, A.; Carril, M.; Norrby, P.-O.; Bolm, C. Copper-Catalyzed Cross-Couplings with Part-per-Million Catalyst Loadings. Angew. Chem., Int. Ed. 2009, 48, 56915693, DOI: 10.1002/anie.200902236 .
    (k) Larsson, P.-F.; Bolm, C.; Norrby, P.-O. Kinetic Investigation of a Ligand-Accelerated Sub-mol% Copper-Catalyzed C-N Cross-Coupling Reaction. Chem. - Eur. J. 2010, 16, 1361313616, DOI: 10.1002/chem.201002021 .
    (l) Larsson, P.-F.; Wallentin, C.-J.; Norrby, P.-O. Mechanistic Aspects of Submol% Copper-Catalyzed CN Cross-Coupling. ChemCatChem 2014, 6, 12771282, DOI: 10.1002/cctc.201301088 .
    (m) Correa, A.; Bolm, C. Iron-Catalyzed N-Arylation of Nitrogen Nucleophiles. Angew. Chem., Int. Ed. 2007, 46, 88628865, DOI: 10.1002/anie.200703299
  7. 7
    (a) Ritleng, V.; Henrion, M.; Chetcuti, M. J. Nickel N-Heterocyclic Carbene-Catalyzed C–Heteroatom Bond Formation, Reduction, and Oxidation: Reactions and Mechanistic Aspects. ACS Catal. 2016, 6, 890906, DOI: 10.1021/acscatal.5b02021 .
    (b) Barker, T. J.; Jarvo, E. R. Umpolung Amination: Nickel-Catalyzed Coupling Reactions of N,N-Dialkyl-N-chloroamines with Diorganozinc Reagents. J. Am. Chem. Soc. 2009, 131, 1559815599, DOI: 10.1021/ja907038b .
    (c) Ilies, L.; Matsubara, T.; Nakamura, E. Nickel-Catalyzed Synthesis of Diarylamines via Oxidatively Induced C–N Bond Formation at Room Temperature. Org. Lett. 2012, 14, 55705573, DOI: 10.1021/ol302688u .
    (d) Shimasaki, T.; Tobisu, M.; Chatani, N. Nickel-Catalyzed Amination of Aryl Pivalates by the Cleavage of Aryl C-O Bonds. Angew. Chem., Int. Ed. 2010, 49, 29292932, DOI: 10.1002/anie.200907287 .
    (e) Iglesias, M. J.; Prieto, A.; Nicasio, M. S. Well-Defined Allylnickel Chloride/N-Heterocyclic Carbene [(NHC)Ni(allyl)Cl] Complexes as Highly Active Precatalysts for C-N and C-S Cross-Coupling Reactions. Adv. Synth. Catal. 2010, 352, 19491954, DOI: 10.1002/adsc.201000223 .
    (f) Rull, S. G.; Blandez, J. F.; Fructos, M. R.; Belderrain, T. R.; Nicasio, M. C. C-N Coupling of Indoles and Carbazoles with Aromatic Chlorides Catalyzed by a Single-Component NHC-Nickel(0) Precursor. Adv. Synth. Catal. 2015, 357, 907911, DOI: 10.1002/adsc.201500030
  8. 8
    (a) Chirik, P. J.; Wieghardt, K. Radical Ligands Confer Nobility on Base-metal Catalysts. Science 2010, 327, 794795, DOI: 10.1126/science.1183281 .
    (b) Broere, D. J. L.; Plessius, R.; van der Vlugt, J. I. New Avenues for Ligand-mediated Processes – Expanding Metal Reactivity by the use of Redox-active Catechol, o-Aminophenol and o-Phenylenediamine Ligands. Chem. Soc. Rev. 2015, 44, 68866915, DOI: 10.1039/C5CS00161G .
    (c) Luca, O. R.; Crabtree, R. H. Redox-active Ligands in Catalysis. Chem. Soc. Rev. 2013, 42, 14401459, DOI: 10.1039/C2CS35228A .
    (d) Lyaskovskyy, V.; de Bruin, B. Redox Non-Innocent Ligands: Versatile New Tools to Control Catalytic Reactions. ACS Catal. 2012, 2, 270279, DOI: 10.1021/cs200660v .
    (e) de Bruin, B.; Gualco, P.; Paul, N. D. In Ligand Design In Metal Chemistry: Reactivity and Catalysis; Stradiotto, M., Lundgren, R., Eds.; Wiley: New York, 2015.
    (f) Smith, A. L.; Hardcastle, K. I.; Soper, J. D. Redox-Active Ligand-Mediated Oxidative Addition and Reductive Elimination at Square Planar Cobalt(III): Multielectron Reactions for Cross-Coupling. J. Am. Chem. Soc. 2010, 132, 1435814360, DOI: 10.1021/ja106212w .
    (g) Sylvester, K. J.; Chirik, P. J. Iron-Catalyzed, Hydrogen-Mediated Reductive Cyclization of 1,6-Enynes and Diynes: Evidence for Bis(imino)pyridine Ligand Participation. J. Am. Chem. Soc. 2009, 131, 87728774, DOI: 10.1021/ja902478p .
    (h) Bouwkamp, M. W.; Bowman, A. C.; Lobkovsky, E.; Chirik, P. J. Iron-Catalyzed [2π + 2π] Cycloaddition of α,ω -Dienes: The Importance of Redox-Active Supporting Ligands. J. Am. Chem. Soc. 2006, 128, 1334013341, DOI: 10.1021/ja064711u .
    (i) Yu, R. P.; Darmon, J. M.; Hoyt, J. M.; Margulieux, G. W.; Turner, Z. R.; Chirik, P. J. High-Activity Iron Catalysts for the Hydrogenation of Hindered, Unfunctionalized Alkenes. ACS Catal. 2012, 2, 17601764, DOI: 10.1021/cs300358m .
    (j) Huang, Y.; Moret, M.-E.; Klein Gebbink, R. J. M. Iron-Mediated Direct Arylation of Unactivated Arenes in Air. Eur. J. Org. Chem. 2014, 2014, 3788, DOI: 10.1002/ejoc.201301620
  9. 9
    (a) Schmidt, V. A.; Kennedy, C. R.; Bezdek, M. J.; Chirik, P. J. Selective [1,4]-Hydrovinylation of 1,3-Dienes with Unactivated Olefins Enabled by Iron Diimine Catalysts. J. Am. Chem. Soc. 2018, 140, 34433453, DOI: 10.1021/jacs.8b00245 .
    (b) Margulieux, G. W.; Bezdek, M. J.; Turner, Z. R.; Chirik, P. J. Ammonia Activation, H2 Evolution and Nitride Formation from a Molybdenum Complex with a Chemically and Redox Noninnocent Ligand. J. Am. Chem. Soc. 2017, 139, 61106113, DOI: 10.1021/jacs.7b03070 .
    (c) Schaefer, B. A.; Margulieux, G. W.; Tiedemann, M. A.; Small, B. L.; Chirik, P. J. Synthesis and Electronic Structure of Iron Borate Betaine Complexes as a Route to Single-Component Iron Ethylene Oligomerization and Polymerization Catalysts. Organometallics 2015, 34, 56155623, DOI: 10.1021/acs.organomet.5b00839 .
    (d) Chirik, P. J. Iron- and Cobalt-Catalyzed Alkene Hydrogenation: Catalysis with Both Redox-Active and Strong Field Ligands. Acc. Chem. Res. 2015, 48, 16871695, DOI: 10.1021/acs.accounts.5b00134 .
    (e) Schmidt, V. A.; Hoyt, J. M.; Margulieux, G. W.; Chirik, P. J. Cobalt-Catalyzed [2π + 2π] Cycloadditions of Alkenes: Scope, Mechanism, and Elucidation of Electronic Structure of Catalytic Intermediates. J. Am. Chem. Soc. 2015, 137, 79037914, DOI: 10.1021/jacs.5b04034
  10. 10
    (a) Bagh, B.; Broere, D. L. J.; Sinha, V.; Kuijpers, P. F.; van Leest, N. P.; de Bruin, B.; Demeshko, S.; Siegler, M. A.; van der Vlugt, J. I. Catalytic Synthesis of N-Heterocycles via Direct C(sp3)-H Amination using an Air-stable Iron(III) Species with a Redox-Active Ligand. J. Am. Chem. Soc. 2017, 139, 51175124, DOI: 10.1021/jacs.7b00270 .
    (b) Broere, D.; de Bruin, B.; Reek, J. N. H.; Lutz, M.; Dechert, S.; van der Vlugt, J. I. Intramolecular Redox-Active Ligand-to-Substrate Single Electron Transfer: Radical Reactivity with a Palladium(II) Complex. J. Am. Chem. Soc. 2014, 136, 1157411577, DOI: 10.1021/ja502164f .
    (c) Smith, A. L.; Hardcastle, K. I.; Soper, J. D. Redox-Active Ligand-Mediated Oxidative Addition and Reductive Elimination at Square Planar Cobalt(III): Multielectron Reactions for Cross-Coupling. J. Am. Chem. Soc. 2010, 132, 1435814360, DOI: 10.1021/ja106212w .
    (d) Blackmore, K. J.; Lal, N.; Ziller, J. W.; Heyduk, A. F. Catalytic Reactivity of a Zirconium(IV) Redox-Active Ligand Complex with 1,2-Diphenylhydrazine. J. Am. Chem. Soc. 2008, 130, 27282729, DOI: 10.1021/ja710611v .
    (e) Rhinehart, J. L.; Mitchell, N. E.; Long, B. K. Enhancing α-Diimine Catalysts for High-Temperature Ethylene Polymerization. ACS Catal. 2014, 4, 25012504, DOI: 10.1021/cs500694m .
    (f) Sikari, R.; Sinha, S.; Jash, U.; Das, S.; Brandaõ, P.; de Bruin, B.; Paul, N. D. Deprotonation Induced Ligand Oxidation in a NiII Complex of a Redox Noninnocent N1-(2-Aminophenyl)benzene-1,2-diamine and Its Use in Catalytic Alcohol Oxidation. Inorg. Chem. 2016, 55, 61146123, DOI: 10.1021/acs.inorgchem.6b00646
  11. 11
    (a) te Grotenhuis, C.; van den Heuvel, N.; van der Vlugt, J. I.; de Bruin, B. Catalytic dibenzocyclooctene synthesis via cobalt(III)-carbene radical and ortho-quinodimethane intermediates. Angew. Chem., Int. Ed. 2018, 57, 140, DOI: 10.1002/anie.201711028 .
    (b) te Grotenhuis, C.; Das, B. G.; Kuijpers, P. F.; Hageman, W.; Trouwborst, M.; de Bruin, B. Catalytic 1,2-Dihydronaphthalene and E-Aryl-Diene Synthesis via CoIII-Carbene Radical and o-Quinodimethane Intermediates. Chemical Science 2017, 8, 82218230, DOI: 10.1039/C7SC03909C .
    (c) Das, B. G.; Chirila, A.; Tromp, M.; Reek, J. N. H; de Bruin, B. CoIII-Carbene Radical Approach to Substituted 1H-Indenes. J. Am. Chem. Soc. 2016, 138, 89688975, DOI: 10.1021/jacs.6b05434 .
    (d) Paul, N. D.; Mandal, S.; Otte, M.; Cui, X.; Zhang, X. P.; de Bruin, B. A. Metalloradical Approach to 2H-Chromenes. J. Am. Chem. Soc. 2014, 136, 10901096, DOI: 10.1021/ja4111336 .
    (e) Paul, N. D.; Chirila, A.; Lu, H.; Zhang, X. P.; de Bruin, B. Carbene Radicals in Cobalt(II) Porphyrin-Catalysed Carbene Carbonylation Reactions; A Catalytic Approach to Ketenes. Chem. - Eur. J. 2013, 19, 1295312958, DOI: 10.1002/chem.201301731
  12. 12
    (a) Sarkar, B.; Kaim, W.; Fiedler, J.; Duboc, C. Molecule-Bridged Mixed-Valent Intermediates Involving the RuI Oxidation State. J. Am. Chem. Soc. 2004, 126, 1470614707, DOI: 10.1021/ja046397e .
    (b) Frantz, S.; Hartmann, H.; Doslik, N.; Wanner, M.; Kaim, W.; Kümmerer, H.; Denninger, G.; Barra, A.; Duboc-Toia, C.; Fiedler, J.; Ciofini, I.; Urban, C.; Kaupp, M. Multifrequency EPR Study and Density Functional g-Tensor Calculations of Persistent Organorhenium Radical Complexes. J. Am. Chem. Soc. 2002, 124, 1056310571, DOI: 10.1021/ja025829n .
    (c) Doslik, N.; Sixt, T.; Kaim, W. The First Structural Characterization of an Azoaromatic Radical Anion Stabilized by Dicopper(I) Coordination. Angew. Chem., Int. Ed. 1998, 37, 24032404, DOI: 10.1002/(SICI)1521-3773(19980918)37:17<2403::AID-ANIE2403>3.0.CO;2-J .
    (d) Shivakumar, M.; Pramanik, K.; Ghosh, P.; Chakravorty, A. Isolation and Structure of the First Azo Anion Radical Complexes of Ruthenium. Inorg. Chem. 1998, 37, 59685969, DOI: 10.1021/ic980719w .
    (e) Sengupta, D.; Ghosh, P.; Chatterjee, T.; Datta, H.; Paul, N. D.; Goswami, S. Ligand-Centered Redox in Nickel(II) Complexes of 2-(Arylazo)pyridine and Isolation of 2-Pyridyl-Substituted Triaryl Hydrazines via Catalytic N-Arylation of Azo-Function. Inorg. Chem. 2014, 53, 1200212013, DOI: 10.1021/ic501656s .
    (f) Joy, S.; Krämer, T.; Paul, N. D.; Banerjee, P.; McGrady, J. E.; Goswami, S. Isolation and Assessment of the Molecular and Electronic Structures of Azo-Anion-Radical Complexes of Chromium and Molybdenum. Experimental and Theoretical Characterization of Complete Electron-Transfer Series. Inorg. Chem. 2011, 50, 999310004, DOI: 10.1021/ic200708c .
    (g) Paul, N. D.; Samanta, S.; Goswami, S. Redox Induced Electron Transfer in Doublet Azo-Anion Diradical Rhenium(II) Complexes. Characterization of Complete Electron Transfer Series. Inorg. Chem. 2010, 49, 26492655, DOI: 10.1021/ic9016195 .
    (h) Paul, N. D.; Samanta, S.; Mondal, T. K.; Goswami, S. Examples of Reductive Azo Cleavage and Oxidative Azo Bond Formation on Re2(CO)10 Template: Isolation and Characterization of Re(III) Complexes of New Azo-Aromatic Ligands. Inorg. Chem. 2011, 50, 78867893, DOI: 10.1021/ic201200r .
    (i) Paul, N. D.; Krämer, T.; McGrady, J. E.; Goswami, S. Dioxygen Activation by Mixed-valent Dirhodium Complexes of Redox Non-innocent Azoaromatic Ligands. Chem. Commun. 2010, 46, 71247126, DOI: 10.1039/c0cc01880e
  13. 13
    (a) Sengupta, D.; Bhattacharjee, R.; Pramanick, R.; Rath, S. P.; Saha Chowdhury, N.; Datta, A.; Goswami, S. Exclusively Ligand-Mediated Catalytic Dehydrogenation of Alcohols. Inorg. Chem. 2016, 55, 96029610, DOI: 10.1021/acs.inorgchem.6b01310 .
    (b) Pramanick, R.; Bhattacharjee, R.; Sengupta, D.; Datta, A.; Goswami, S. An Azoaromatic Ligand as Four Electron Four Proton Reservoir: Catalytic Dehydrogenation of Alcohols by Its Zinc(II) Complex. Inorg. Chem. 2018, 57, 6816, DOI: 10.1021/acs.inorgchem.8b00034
  14. 14
    (a) Sinha, S.; Das, S.; Sikari, R.; Parua, S.; Brandaõ, P.; Demeshko, S.; Meyer, F.; Paul, N. D. Redox Noninnocent Azo-Aromatic Pincers and Their Iron Complexes. Isolation, Characterization, and Catalytic Alcohol Oxidation. Inorg. Chem. 2017, 56, 1408414100, DOI: 10.1021/acs.inorgchem.7b02238 .
    (b) Das, S.; Sinha, S.; Jash, U.; Sikari, R.; Saha, A.; Barman, S. K.; Brandão, P.; Paul, N. D. Redox-Induced Interconversion and Ligand-Centered Hemilability in Ni(II) Complexes of Redox-Noninnocent Azo-Aromatic Pincers. Inorg. Chem. 2018, 57, 58305841, DOI: 10.1021/acs.inorgchem.8b00231
  15. 15
    (a) Barham, J. P.; Coulthard, G.; Emery, K. J.; Doni, E.; Cumine, F.; Nocera, G.; John, M. P.; Berlouis, L. E. A.; McGuire, T.; Tuttle, T.; Murphy, J. A. KOtBu: A Privileged Reagent for Electron Transfer Reactions?. J. Am. Chem. Soc. 2016, 138, 74027410, DOI: 10.1021/jacs.6b03282 .
    (b) Yi, H.; Jutand, A.; Lei, A. Evidence for the Interaction Between tBuOK and 1,10-Phenanthroline to form the 1,10-Phenanthroline Radical Anion: a Key Step for the Activation of Aryl Bromides by Electron Transfer. Chem. Commun. 2015, 51, 545548, DOI: 10.1039/C4CC07299E .
    (c) Cuthbertson, J.; Gray, V. J.; Wilden, J. D. Observations on Transition Metal Free Biaryl Coupling: Potassium tert-Butoxide Alone Promotes the Reaction without Diamine or Phenanthroline Catalysts. Chem. Commun. 2014, 50, 25752578, DOI: 10.1039/C3CC49019J
  16. 16
    (a) Das, C.; Ghosh, A. K.; Hung, C.-H.; Lee, G.-H.; Peng, S.-M.; Goswami, S. Metal-Promoted Aromatic Ring Amination and Deamination Reactions at a Diazo Ligand Coordinated to Rhodium and Ruthenium. Inorg. Chem. 2002, 41, 71257135, DOI: 10.1021/ic020421c .
    (b) Das, C.; Saha, A.; Hung, C.-H.; Lee, G.-H.; Peng, S.-M.; Goswami, S. Ruthenium Complexes of 2-[(4-(Arylamino)phenyl)azo]pyridine Formed via Regioselective Phenyl Ring Amination of Coordinated 2-(Phenylazo)pyridine: Isolation of Products, X-ray Structure, and Redox and Optical Properties. Inorg. Chem. 2003, 42, 198204, DOI: 10.1021/ic0203724 .
    (c) Kamar, K. K.; Das, S.; Hung, C.-H.; Castiñeiras, A.; Kuz’min, M. D.; Rillo, K. C.; Bartolomé, J.; Goswami, S. Design and Synthesis of a New Binucleating Ligand via Cobalt-Promoted C–N Bond Fusion Reaction. Ligand Isolation and Its Coordination to Nickel, Palladium, and Platinum. Inorg. Chem. 2003, 42, 53675375, DOI: 10.1021/ic034313h
  17. 17

    The DFT barriers obtained at the BP86, def2-TZVP DFT-D3 level are rather low and do not explain the elevated temperatures needed in the experimental reactions. There can be several reasons for the need for elevated temperatures in the experimental catalytic reactions such as the presence of (lower energy) dormant species that were not explored computationally. The computational barriers might also be somewhat underestimated. Higher level calculations (using, e.g., meta-GGA functionals) could perhaps lead to somewhat higher barriers. However, exploring these possibilities is beyond the scope of the present paper.

  18. 18

    For nucleophiles where only one nitrogen center is available, the reaction will definitely go through the nitrogen that is bound to the iron center.

  19. 19
    Bruker SAINT-plus; Bruker AXS Inc.: Madison, WI, 2007.
  20. 20
    (a) Sheldrick, G. M. SHELXS-97, A Program for Crystal Structure Solution; University of Göttingen: Göttingen, Germany, 1997.
    (b) Sheldrick, G. M. SHELXL-97, a Program for Crystal Structure Refinement; University of Göttingen: Göttingen, Germany, 1997.
  21. 21
    Sheldrick, G. M. A short history of SHELX. Acta Crystallogr., Sect. A: Found. Crystallogr. 2008, A64, 112122, DOI: 10.1107/S0108767307043930
  22. 22
    Ahlrichs, R. Turbomole Version 6.5; Theoretical Chemistry Group, University of Karlsruhe, 2013.
  23. 23

    PQS version 2.4, 2001, Parallel Quantum Solutions, Fayettevile, Arkansas (USA); the Baker optimizer is available separately from PQS upon request:

    Baker, I. J. Comput. Chem. 1986, 7, 385, DOI: 10.1002/jcc.540070402
  24. 24
    Budzelaar, P. H. M. J. Comput. Chem. 2007, 28, 2226, DOI: 10.1002/jcc.20740
  25. 25
    (a) Becke, A. D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A: At., Mol., Opt. Phys. 1988, 38, 30983100, DOI: 10.1103/PhysRevA.38.3098 .
    (b) Perdew, J. P. Density-functional approximation for the correlation energy of the inhomogeneous electron gas. Phys. Rev. B: Condens. Matter Mater. Phys. 1986, 33, 88228824, DOI: 10.1103/PhysRevB.33.8822
  26. 26
    Sierka, M.; Hogekamp, A.; Ahlrichs, R. Fast evaluation of the Coulomb potential for electron densities using multipole accelerated resolution of identity approximation. J. Chem. Phys. 2003, 118, 91369148, DOI: 10.1063/1.1567253
  27. 27
    Schaefer, A.; Horn, H.; Ahlrichs, R. Fully optimized contracted Gaussian basis sets for atoms Li to Kr. J. Chem. Phys. 1992, 97, 25712577, DOI: 10.1063/1.463096
  28. 28
    Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132 (154104), 119, DOI: 10.1063/1.3382344
  29. 29
    Dzik, W. I.; Xu, X.; Zhang, X. P.; Reek, J. N. H.; de Bruin, B. ‘Carbene Radicals’ in CoII(por)-Catalyzed Olefin Cyclopropanation. J. Am. Chem. Soc. 2010, 132, 1089110902, DOI: 10.1021/ja103768r

Cited By


This article is cited by 6 publications.

  1. Rina Sikari, Suman Sinha, Siuli Das, Anannya Saha, Gargi Chakraborty, Rakesh Mondal, Nanda D. Paul. Achieving Nickel Catalyzed C–S Cross-Coupling under Mild Conditions Using Metal–Ligand Cooperativity. The Journal of Organic Chemistry 2019, 84 (7) , 4072-4085. DOI: 10.1021/acs.joc.9b00075.
  2. Gargi Chakraborty, Rina Sikari, Siuli Das, Rakesh Mondal, Suman Sinha, Seemika Banerjee, Nanda D. Paul. Dehydrogenative Synthesis of Quinolines, 2-Aminoquinolines, and Quinazolines Using Singlet Diradical Ni(II)-Catalysts. The Journal of Organic Chemistry 2019, 84 (5) , 2626-2641. DOI: 10.1021/acs.joc.8b03070.
  3. Jin-Quan Chen, Xing Liu, Jia Guo, Zhi-Bing Dong. A Chemoselective and Desulfurative Chan-Lam Coupling: C-N Bond Formation between Benzimidazoline-2-Thiones and Arylboronic Acids. European Journal of Organic Chemistry 2020, 2020 (16) , 2414-2424. DOI: 10.1002/ejoc.202000075.
  4. Rakesh Mondal, Suman Sinha, Siuli Das, Gargi Chakraborty, Nanda D. Paul. Iron Catalyzed Synthesis of Pyrimidines Under Air. Advanced Synthesis & Catalysis 2020, 362 (3) , 594-600. DOI: 10.1002/adsc.201901172.
  5. Suman Sinha, Siuli Das, Rakesh Mondal, Sutanuva Mandal, Nanda D. Paul. Cobalt complexes of redox noninnocent azo-aromatic pincers. Isolation, characterization, and application as catalysts for the synthesis of quinazolin-4(3 H )-ones. Dalton Transactions 2020, 327 DOI: 10.1039/D0DT00394H.
  6. Rina Sikari, Suman Sinha, Gargi Chakraborty, Siuli Das, Nicolaas Petrus Leest, Nanda D. Paul. C−N Cross‐Coupling Reactions Under Mild Conditions Using Singlet Di‐Radical Nickel(II)‐Complexes as Catalyst: N‐Arylation and Quinazoline Synthesis. Advanced Synthesis & Catalysis 2019, 361 (18) , 4342-4353. DOI: 10.1002/adsc.201900545.
  • Abstract

    Scheme 1

    Scheme 1. Different Chemical Transformations Using Iron Complexes of Redox Noninnocent Ligands

    Scheme 2

    Scheme 2. Synthesis of Catalysts 1a, 1b, 1c and 2a, 2b, 2c

    Scheme 3

    Scheme 3. Competitive C–N Bond Formation Reactions

    Figure 1

    Figure 1. ORTEP representation of L2c with ellipsoids drawn at the 50% probability level. Hydrogen atoms are omitted for clarity (N3–N4: 1.256(3) Å).

    Figure 2

    Figure 2. ORTEP representation of L3c with ellipsoids drawn at the 50% probability level. Hydrogen atoms are omitted for clarity (N3–N4: 1.262(4) Å).

    Scheme 4

    Scheme 4. Ligand Centered C–N Coupling in Absence of Substrate (Iodobenzene)

    Neat conditions.

    Scheme 5

    Scheme 5. Proposed Mechanism

    Scheme 6

    Scheme 6. Computed Pathway for Substrate Activation by Cleavage of Aryl–Iodide Bond in Ar–I

    Scheme 7

    Scheme 7. Computed Pathway for Ar–Nu Coupling after Ar–I Bond Activation

    Scheme 8

    Scheme 8. Release of Ar–Nu and Catalyst Regeneration
  • References

    ARTICLE SECTIONS
    Jump To

    This article references 29 other publications.

    1. 1
      (a) Hili, R.; Yudin, A. K. Making Carbon-nitrogen Bonds in Biological and Chemical Synthesis. Nat. Chem. Biol. 2006, 2, 284287, DOI: 10.1038/nchembio0606-284 .
      (b) Ullmann, F. Ueber eine neue bildungsweise von diphenylaminderivaten. Ber. Dtsch. Chem. Ges. 1903, 36, 23822384, DOI: 10.1002/cber.190303602174 .
      (c) Goldberg, I. Ueber Phenylirungen Bei Gegenwart von Kupfer als Katalysator. Ber. Dtsch. Chem. Ges. 1906, 39, 16911692, DOI: 10.1002/cber.19060390298 .
      (d) Barton, D. H. R.; Nakanishi, K.; Meth-Cohn, O. Comprehensive Natural Products Chemistry; Elsevier: Oxford, 1999; Vol. 4.
      (e) Ricci, A. Amino Group Chemistry, From Synthesis to the Life Sciences; Wiley-VCH: Weinheim, 2007.
      (f) Bariwal, J.; Van der Eycken, E. C–N bond forming cross-coupling reactions: an overview. Chem. Soc. Rev. 2013, 42, 92839303, DOI: 10.1039/c3cs60228a .
      (g) Shin, K.; Kim, H.; Chang, S. Transition-Metal-Catalyzed C–N Bond Forming Reactions Using Organic Azides as the Nitrogen Source: A Journey for the Mild and Versatile C–H Amination. Acc. Chem. Res. 2015, 48, 10401052, DOI: 10.1021/acs.accounts.5b00020 .
      (h) Park, Y.; Kim, Y.; Chang, S. Transition Metal-Catalyzed C–H Amination: Scope, Mechanism, and Applications. Chem. Rev. 2017, 117, 92479301, DOI: 10.1021/acs.chemrev.6b00644
    2. 2
      (a) Craig, P. N. Comprehensive Medicinal Chemistry; Drayton, C. J., Ed.; Pergamon Press: New York, 1991; Vol. 8.
      (b) Cozzi, P.; Carganico, G.; Fusar, D.; Grossoni, M.; Menichincheri, M.; Pinciroli, V.; Tonani, R.; Vaghi, F.; Salvati, P. Imidazol-1-yl and pyridin-3-yl derivatives of 4-phenyl-1,4-dihydropyridines combining Ca2+ antagonism and thromboxane A2 synthase inhibition. J. Med. Chem. 1993, 36, 29642972, DOI: 10.1021/jm00072a017 .
      (c) Katritzky, A. R.; Rees, C. W.; Scriven, E. F. V. Comprehensive Heterocyclic Chemistry II; Elsevier: Oxford, 1996.
      (d) Fairlamb, I. J. S. Regioselective (site-selective) Functionalisation of Unsaturated Halogenated Nitrogen, Oxygen and Sulfur Heterocycles by Pd-catalysed Cross-couplings and Direct Arylation Processes. Chem. Soc. Rev. 2007, 36, 10361045, DOI: 10.1039/b611177g
    3. 3
      (a) Ruiz-Castillo, P.; Buchwald, S. L. Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions. Chem. Rev. 2016, 116, 1256412649, DOI: 10.1021/acs.chemrev.6b00512 .
      (b) Ueda, S.; Su, M.; Buchwald, S. L. Completely N1-Selective Palladium-Catalyzed Arylation of Unsymmetric Imidazoles: Application to the Synthesis of Nilotinib. J. Am. Chem. Soc. 2012, 134, 700706, DOI: 10.1021/ja2102373 .
      (c) Shuler, S. A.; Yin, G.; Krause, S. B.; Vesper, C. M.; Watson, D. A. Synthesis of Secondary Unsaturated Lactams via an Aza-Heck Reaction. J. Am. Chem. Soc. 2016, 138, 1383013833, DOI: 10.1021/jacs.6b08932 .
      (d) Khatun, N.; Modi, A.; Ali, W.; Patel, B. K. Palladium-Catalyzed Synthesis of 2-Aryl-2H-Benzotriazoles from Azoarenes and TMSN3. J. Org. Chem. 2015, 80, 96629670, DOI: 10.1021/acs.joc.5b01706 .
      (e) Zhou, Y.; Verkade, J. G. Highly Efficient Ligands for the Palladium-Assisted Double N-Arylation of Primary Amines for One-Sep Construction of Carbazoles. Adv. Synth. Catal. 2010, 352, 616620, DOI: 10.1002/adsc.200900846 .
      (f) Ikawa, T.; Barder, T. E.; Biscoe, M. R.; Buchwald, S. L. Pd-Catalyzed Amidations of Aryl Chlorides Using Monodentate Biaryl Phosphine Ligands: A Kinetic, Computational, and Synthetic Investigation. J. Am. Chem. Soc. 2007, 129, 1300113007, DOI: 10.1021/ja0717414 .
      (g) Hicks, J. D.; Hyde, A. M.; Cuezva, A. M.; Buchwald, S. L. Pd-Catalyzed N-Arylation of Secondary Acyclic Amides: Catalyst Development, Scope, and Computational Study. J. Am. Chem. Soc. 2009, 131, 1672016734, DOI: 10.1021/ja9044357 .
      (h) Beletskaya, I. P.; Cheprakov, A. V. The Complementary Competitors: Palladium and Copper in C–N Cross-Coupling Reactions. Organometallics 2012, 31, 77537808, DOI: 10.1021/om300683c .
      (i) Vo, G. D.; Hartwig, J. F. Palladium-Catalyzed Coupling of Ammonia with Aryl Chlorides, Bromides, Iodides, and Sulfonates: A General Method for the Preparation of Primary Arylamines. J. Am. Chem. Soc. 2009, 131, 1104911061, DOI: 10.1021/ja903049z .
      (j) Brusoe, A. T.; Hartwig, J. F. Palladium-Catalyzed Arylation of Fluoroalkylamines. J. Am. Chem. Soc. 2015, 137, 84608468, DOI: 10.1021/jacs.5b02512 .
      (k) Green, R. A.; Hartwig, J. F. Palladium-Catalyzed Amination of Aryl Chlorides and Bromides with Ammonium Salts. Org. Lett. 2014, 16, 43884391, DOI: 10.1021/ol501739g
    4. 4
      (a) Wang, H.; Yu, Y.; Hong, X.; Tan, Q.; Xu, B. Rhodium-Catalyzed Direct ortho C–N Bond Formation of Aromatic Azo Compounds with Azides. J. Org. Chem. 2014, 79, 32793288, DOI: 10.1021/jo500412w .
      (b) Andersson, P. G.; Dauban, P.; Lescot, C.; Diaz-Requejo, M. M.; Perez, P. J. Rh-, Ag-, and Cu-Catalyzed C–N Bond Formation. Innovative Catalysis in Organic Synthesis: Oxidation, Hydrogenation, and C-X Bond Forming Reactions; Wiley, 2012. DOI: DOI: 10.1002/9783527646586.ch12 .
      (c) Song, G.; Wang, F.; Li, X. C–C, C–O and C–N bond formation via rhodium(III)-catalyzed oxidative C–H activation. Chem. Soc. Rev. 2012, 41, 36513678, DOI: 10.1039/c2cs15281a .
      (d) Tang, C.; Yuan, Y.; Cui, Y.; Jiao, N. Rh-Catalyzed Diarylamine Synthesis by Intermolecular C–H Amination of Heteroarylarenes. Eur. J. Org. Chem. 2013, 2013, 74807483, DOI: 10.1002/ejoc.201301430
    5. 5
      (a) Yi, C. S. Recent Advances in the Synthetic and Mechanistic Aspects of the Ruthenium-Catalyzed Carbon-heteroatom Bond Forming Reactions of Alkenes and Alkynes. J. Organomet. Chem. 2011, 696, 7680, DOI: 10.1016/j.jorganchem.2010.08.002 .
      (b) Ackermann, L.; Lygin, A. V.; Hofmann, N. Ruthenium-Catalyzed Oxidative Synthesis of 2-Pyridones through C–H/N–H Bond Functionalizations. Org. Lett. 2011, 13, 32783281, DOI: 10.1021/ol201244s .
      (c) Huang, L.; Arndt, M.; Gooßen, K.; Heydt, H.; Gooßen, L. Late Transition Metal-Catalyzed Hydroamination and Hydroamidation. Chem. Rev. 2015, 115, 25962697, DOI: 10.1021/cr300389u .
      (d) Arockiam, P. B.; Bruneau, C.; Dixneuf, P. H. Ruthenium(II)-Catalyzed C–H Bond Activation and Functionalization. Chem. Rev. 2012, 112, 58795918, DOI: 10.1021/cr300153j .
      (e) Utsunomiya, M.; Hartwig, J. F. Ruthenium-Catalyzed Anti-Markovnikov Hydroamination of Vinylarenes. J. Am. Chem. Soc. 2004, 126, 27022703, DOI: 10.1021/ja031542u .
      (f) Takemiya, A.; Hartwig, J. F. Rhodium-Catalyzed Intramolecular, Anti-MarkovnikovHydroamination. Synthesis of 3-Arylpiperidines. J. Am. Chem. Soc. 2006, 128, 60426043, DOI: 10.1021/ja058299e .
      (g) Wu, L.; Fleischer, I.; Jackstell, R.; Beller, M. Efficient and Regioselective Ruthenium-catalyzed Hydro-aminomethylation of Olefins. J. Am. Chem. Soc. 2013, 135, 39893996, DOI: 10.1021/ja312271c
    6. 6
      (a) Antilla, J. C.; Klapars, A.; Buchwald, S. L. The Copper-Catalyzed N-Arylation of Indoles. J. Am. Chem. Soc. 2002, 124, 1168411688, DOI: 10.1021/ja027433h .
      (b) Davis, O. A.; Hughes, M.; Bull, J. A. Copper-Catalyzed N-Arylation of 2-Imidazolines with Aryl Iodides. J. Org. Chem. 2013, 78, 34703475, DOI: 10.1021/jo400120r .
      (c) Kim, H.; Chang, S. Transition-Metal-Mediated Direct C–H Amination of Hydrocarbons with Amine Reactants: The Most Desirable but Challenging C–N Bond-Formation Approach. ACS Catal. 2016, 6, 23412351, DOI: 10.1021/acscatal.6b00293 .
      (d) Rasheed, S.; Rao, D. N.; Das, P. Copper-Catalyzed Inter- and Intramolecular C–N Bond Formation: Synthesis of Benzimidazole-Fused Heterocycles. J. Org. Chem. 2015, 80, 93219327, DOI: 10.1021/acs.joc.5b01396 .
      (e) Stabile, P.; Lamonica, A.; Ribecai, A.; Castoldi, D.; Guercio, G.; Curcuruto, O. Mild, convenient and versatile Cu-mediated synthesis of N-aryl-2-imidazolidinones. Tetrahedron Lett. 2010, 51, 32323235, DOI: 10.1016/j.tetlet.2010.04.064 .
      (f) Hartwig, J. F. Evolution of a Fourth Generation Catalyst for the Amination and Thioetherification of Aryl Halides. Acc. Chem. Res. 2008, 41, 15341544, DOI: 10.1021/ar800098p .
      (g) Strieter, E. R.; Bhayana, B.; Buchwald, S. L. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides. J. Am. Chem. Soc. 2009, 131, 7888, DOI: 10.1021/ja0781893 .
      (h) Zhu, L.; Cheng, L.; Zhang, Y.; Xie, R.; You, J. Highly Efficient Copper-Catalyzed N-Arylation of Nitrogen-Containing Heterocycles with Aryl and Heteroaryl Halides. J. Org. Chem. 2007, 72, 27372743, DOI: 10.1021/jo062059f .
      (i) Buchwald, S. L.; Bolm, C. On the Role of Metal Contaminants in Catalyses with FeCl3. Angew. Chem., Int. Ed. 2009, 48, 55865587, DOI: 10.1002/anie.200902237 .
      (j) Larsson, P.-F.; Correa, A.; Carril, M.; Norrby, P.-O.; Bolm, C. Copper-Catalyzed Cross-Couplings with Part-per-Million Catalyst Loadings. Angew. Chem., Int. Ed. 2009, 48, 56915693, DOI: 10.1002/anie.200902236 .
      (k) Larsson, P.-F.; Bolm, C.; Norrby, P.-O. Kinetic Investigation of a Ligand-Accelerated Sub-mol% Copper-Catalyzed C-N Cross-Coupling Reaction. Chem. - Eur. J. 2010, 16, 1361313616, DOI: 10.1002/chem.201002021 .
      (l) Larsson, P.-F.; Wallentin, C.-J.; Norrby, P.-O. Mechanistic Aspects of Submol% Copper-Catalyzed CN Cross-Coupling. ChemCatChem 2014, 6, 12771282, DOI: 10.1002/cctc.201301088 .
      (m) Correa, A.; Bolm, C. Iron-Catalyzed N-Arylation of Nitrogen Nucleophiles. Angew. Chem., Int. Ed. 2007, 46, 88628865, DOI: 10.1002/anie.200703299
    7. 7
      (a) Ritleng, V.; Henrion, M.; Chetcuti, M. J. Nickel N-Heterocyclic Carbene-Catalyzed C–Heteroatom Bond Formation, Reduction, and Oxidation: Reactions and Mechanistic Aspects. ACS Catal. 2016, 6, 890906, DOI: 10.1021/acscatal.5b02021 .
      (b) Barker, T. J.; Jarvo, E. R. Umpolung Amination: Nickel-Catalyzed Coupling Reactions of N,N-Dialkyl-N-chloroamines with Diorganozinc Reagents. J. Am. Chem. Soc. 2009, 131, 1559815599, DOI: 10.1021/ja907038b .
      (c) Ilies, L.; Matsubara, T.; Nakamura, E. Nickel-Catalyzed Synthesis of Diarylamines via Oxidatively Induced C–N Bond Formation at Room Temperature. Org. Lett. 2012, 14, 55705573, DOI: 10.1021/ol302688u .
      (d) Shimasaki, T.; Tobisu, M.; Chatani, N. Nickel-Catalyzed Amination of Aryl Pivalates by the Cleavage of Aryl C-O Bonds. Angew. Chem., Int. Ed. 2010, 49, 29292932, DOI: 10.1002/anie.200907287 .
      (e) Iglesias, M. J.; Prieto, A.; Nicasio, M. S. Well-Defined Allylnickel Chloride/N-Heterocyclic Carbene [(NHC)Ni(allyl)Cl] Complexes as Highly Active Precatalysts for C-N and C-S Cross-Coupling Reactions. Adv. Synth. Catal. 2010, 352, 19491954, DOI: 10.1002/adsc.201000223 .
      (f) Rull, S. G.; Blandez, J. F.; Fructos, M. R.; Belderrain, T. R.; Nicasio, M. C. C-N Coupling of Indoles and Carbazoles with Aromatic Chlorides Catalyzed by a Single-Component NHC-Nickel(0) Precursor. Adv. Synth. Catal. 2015, 357, 907911, DOI: 10.1002/adsc.201500030
    8. 8
      (a) Chirik, P. J.; Wieghardt, K. Radical Ligands Confer Nobility on Base-metal Catalysts. Science 2010, 327, 794795, DOI: 10.1126/science.1183281 .
      (b) Broere, D. J. L.; Plessius, R.; van der Vlugt, J. I. New Avenues for Ligand-mediated Processes – Expanding Metal Reactivity by the use of Redox-active Catechol, o-Aminophenol and o-Phenylenediamine Ligands. Chem. Soc. Rev. 2015, 44, 68866915, DOI: 10.1039/C5CS00161G .
      (c) Luca, O. R.; Crabtree, R. H. Redox-active Ligands in Catalysis. Chem. Soc. Rev. 2013, 42, 14401459, DOI: 10.1039/C2CS35228A .
      (d) Lyaskovskyy, V.; de Bruin, B. Redox Non-Innocent Ligands: Versatile New Tools to Control Catalytic Reactions. ACS Catal. 2012, 2, 270279, DOI: 10.1021/cs200660v .
      (e) de Bruin, B.; Gualco, P.; Paul, N. D. In Ligand Design In Metal Chemistry: Reactivity and Catalysis; Stradiotto, M., Lundgren, R., Eds.; Wiley: New York, 2015.
      (f) Smith, A. L.; Hardcastle, K. I.; Soper, J. D. Redox-Active Ligand-Mediated Oxidative Addition and Reductive Elimination at Square Planar Cobalt(III): Multielectron Reactions for Cross-Coupling. J. Am. Chem. Soc. 2010, 132, 1435814360, DOI: 10.1021/ja106212w .
      (g) Sylvester, K. J.; Chirik, P. J. Iron-Catalyzed, Hydrogen-Mediated Reductive Cyclization of 1,6-Enynes and Diynes: Evidence for Bis(imino)pyridine Ligand Participation. J. Am. Chem. Soc. 2009, 131, 87728774, DOI: 10.1021/ja902478p .
      (h) Bouwkamp, M. W.; Bowman, A. C.; Lobkovsky, E.; Chirik, P. J. Iron-Catalyzed [2π + 2π] Cycloaddition of α,ω -Dienes: The Importance of Redox-Active Supporting Ligands. J. Am. Chem. Soc. 2006, 128, 1334013341, DOI: 10.1021/ja064711u .
      (i) Yu, R. P.; Darmon, J. M.; Hoyt, J. M.; Margulieux, G. W.; Turner, Z. R.; Chirik, P. J. High-Activity Iron Catalysts for the Hydrogenation of Hindered, Unfunctionalized Alkenes. ACS Catal. 2012, 2, 17601764, DOI: 10.1021/cs300358m .
      (j) Huang, Y.; Moret, M.-E.; Klein Gebbink, R. J. M. Iron-Mediated Direct Arylation of Unactivated Arenes in Air. Eur. J. Org. Chem. 2014, 2014, 3788, DOI: 10.1002/ejoc.201301620
    9. 9
      (a) Schmidt, V. A.; Kennedy, C. R.; Bezdek, M. J.; Chirik, P. J. Selective [1,4]-Hydrovinylation of 1,3-Dienes with Unactivated Olefins Enabled by Iron Diimine Catalysts. J. Am. Chem. Soc. 2018, 140, 34433453, DOI: 10.1021/jacs.8b00245 .
      (b) Margulieux, G. W.; Bezdek, M. J.; Turner, Z. R.; Chirik, P. J. Ammonia Activation, H2 Evolution and Nitride Formation from a Molybdenum Complex with a Chemically and Redox Noninnocent Ligand. J. Am. Chem. Soc. 2017, 139, 61106113, DOI: 10.1021/jacs.7b03070 .
      (c) Schaefer, B. A.; Margulieux, G. W.; Tiedemann, M. A.; Small, B. L.; Chirik, P. J. Synthesis and Electronic Structure of Iron Borate Betaine Complexes as a Route to Single-Component Iron Ethylene Oligomerization and Polymerization Catalysts. Organometallics 2015, 34, 56155623, DOI: 10.1021/acs.organomet.5b00839 .
      (d) Chirik, P. J. Iron- and Cobalt-Catalyzed Alkene Hydrogenation: Catalysis with Both Redox-Active and Strong Field Ligands. Acc. Chem. Res. 2015, 48, 16871695, DOI: 10.1021/acs.accounts.5b00134 .
      (e) Schmidt, V. A.; Hoyt, J. M.; Margulieux, G. W.; Chirik, P. J. Cobalt-Catalyzed [2π + 2π] Cycloadditions of Alkenes: Scope, Mechanism, and Elucidation of Electronic Structure of Catalytic Intermediates. J. Am. Chem. Soc. 2015, 137, 79037914, DOI: 10.1021/jacs.5b04034
    10. 10
      (a) Bagh, B.; Broere, D. L. J.; Sinha, V.; Kuijpers, P. F.; van Leest, N. P.; de Bruin, B.; Demeshko, S.; Siegler, M. A.; van der Vlugt, J. I. Catalytic Synthesis of N-Heterocycles via Direct C(sp3)-H Amination using an Air-stable Iron(III) Species with a Redox-Active Ligand. J. Am. Chem. Soc. 2017, 139, 51175124, DOI: 10.1021/jacs.7b00270 .
      (b) Broere, D.; de Bruin, B.; Reek, J. N. H.; Lutz, M.; Dechert, S.; van der Vlugt, J. I. Intramolecular Redox-Active Ligand-to-Substrate Single Electron Transfer: Radical Reactivity with a Palladium(II) Complex. J. Am. Chem. Soc. 2014, 136, 1157411577, DOI: 10.1021/ja502164f .
      (c) Smith, A. L.; Hardcastle, K. I.; Soper, J. D. Redox-Active Ligand-Mediated Oxidative Addition and Reductive Elimination at Square Planar Cobalt(III): Multielectron Reactions for Cross-Coupling. J. Am. Chem. Soc. 2010, 132, 1435814360, DOI: 10.1021/ja106212w .
      (d) Blackmore, K. J.; Lal, N.; Ziller, J. W.; Heyduk, A. F. Catalytic Reactivity of a Zirconium(IV) Redox-Active Ligand Complex with 1,2-Diphenylhydrazine. J. Am. Chem. Soc. 2008, 130, 27282729, DOI: 10.1021/ja710611v .
      (e) Rhinehart, J. L.; Mitchell, N. E.; Long, B. K. Enhancing α-Diimine Catalysts for High-Temperature Ethylene Polymerization. ACS Catal. 2014, 4, 25012504, DOI: 10.1021/cs500694m .
      (f) Sikari, R.; Sinha, S.; Jash, U.; Das, S.; Brandaõ, P.; de Bruin, B.; Paul, N. D. Deprotonation Induced Ligand Oxidation in a NiII Complex of a Redox Noninnocent N1-(2-Aminophenyl)benzene-1,2-diamine and Its Use in Catalytic Alcohol Oxidation. Inorg. Chem. 2016, 55, 61146123, DOI: 10.1021/acs.inorgchem.6b00646
    11. 11
      (a) te Grotenhuis, C.; van den Heuvel, N.; van der Vlugt, J. I.; de Bruin, B. Catalytic dibenzocyclooctene synthesis via cobalt(III)-carbene radical and ortho-quinodimethane intermediates. Angew. Chem., Int. Ed. 2018, 57, 140, DOI: 10.1002/anie.201711028 .
      (b) te Grotenhuis, C.; Das, B. G.; Kuijpers, P. F.; Hageman, W.; Trouwborst, M.; de Bruin, B. Catalytic 1,2-Dihydronaphthalene and E-Aryl-Diene Synthesis via CoIII-Carbene Radical and o-Quinodimethane Intermediates. Chemical Science 2017, 8, 82218230, DOI: 10.1039/C7SC03909C .
      (c) Das, B. G.; Chirila, A.; Tromp, M.; Reek, J. N. H; de Bruin, B. CoIII-Carbene Radical Approach to Substituted 1H-Indenes. J. Am. Chem. Soc. 2016, 138, 89688975, DOI: 10.1021/jacs.6b05434 .
      (d) Paul, N. D.; Mandal, S.; Otte, M.; Cui, X.; Zhang, X. P.; de Bruin, B. A. Metalloradical Approach to 2H-Chromenes. J. Am. Chem. Soc. 2014, 136, 10901096, DOI: 10.1021/ja4111336 .
      (e) Paul, N. D.; Chirila, A.; Lu, H.; Zhang, X. P.; de Bruin, B. Carbene Radicals in Cobalt(II) Porphyrin-Catalysed Carbene Carbonylation Reactions; A Catalytic Approach to Ketenes. Chem. - Eur. J. 2013, 19, 1295312958, DOI: 10.1002/chem.201301731
    12. 12
      (a) Sarkar, B.; Kaim, W.; Fiedler, J.; Duboc, C. Molecule-Bridged Mixed-Valent Intermediates Involving the RuI Oxidation State. J. Am. Chem. Soc. 2004, 126, 1470614707, DOI: 10.1021/ja046397e .
      (b) Frantz, S.; Hartmann, H.; Doslik, N.; Wanner, M.; Kaim, W.; Kümmerer, H.; Denninger, G.; Barra, A.; Duboc-Toia, C.; Fiedler, J.; Ciofini, I.; Urban, C.; Kaupp, M. Multifrequency EPR Study and Density Functional g-Tensor Calculations of Persistent Organorhenium Radical Complexes. J. Am. Chem. Soc. 2002, 124, 1056310571, DOI: 10.1021/ja025829n .
      (c) Doslik, N.; Sixt, T.; Kaim, W. The First Structural Characterization of an Azoaromatic Radical Anion Stabilized by Dicopper(I) Coordination. Angew. Chem., Int. Ed. 1998, 37, 24032404, DOI: 10.1002/(SICI)1521-3773(19980918)37:17<2403::AID-ANIE2403>3.0.CO;2-J .
      (d) Shivakumar, M.; Pramanik, K.; Ghosh, P.; Chakravorty, A. Isolation and Structure of the First Azo Anion Radical Complexes of Ruthenium. Inorg. Chem. 1998, 37, 59685969, DOI: 10.1021/ic980719w .
      (e) Sengupta, D.; Ghosh, P.; Chatterjee, T.; Datta, H.; Paul, N. D.; Goswami, S. Ligand-Centered Redox in Nickel(II) Complexes of 2-(Arylazo)pyridine and Isolation of 2-Pyridyl-Substituted Triaryl Hydrazines via Catalytic N-Arylation of Azo-Function. Inorg. Chem. 2014, 53, 1200212013, DOI: 10.1021/ic501656s .
      (f) Joy, S.; Krämer, T.; Paul, N. D.; Banerjee, P.; McGrady, J. E.; Goswami, S. Isolation and Assessment of the Molecular and Electronic Structures of Azo-Anion-Radical Complexes of Chromium and Molybdenum. Experimental and Theoretical Characterization of Complete Electron-Transfer Series. Inorg. Chem. 2011, 50, 999310004, DOI: 10.1021/ic200708c .
      (g) Paul, N. D.; Samanta, S.; Goswami, S. Redox Induced Electron Transfer in Doublet Azo-Anion Diradical Rhenium(II) Complexes. Characterization of Complete Electron Transfer Series. Inorg. Chem. 2010, 49, 26492655, DOI: 10.1021/ic9016195 .
      (h) Paul, N. D.; Samanta, S.; Mondal, T. K.; Goswami, S. Examples of Reductive Azo Cleavage and Oxidative Azo Bond Formation on Re2(CO)10 Template: Isolation and Characterization of Re(III) Complexes of New Azo-Aromatic Ligands. Inorg. Chem. 2011, 50, 78867893, DOI: 10.1021/ic201200r .
      (i) Paul, N. D.; Krämer, T.; McGrady, J. E.; Goswami, S. Dioxygen Activation by Mixed-valent Dirhodium Complexes of Redox Non-innocent Azoaromatic Ligands. Chem. Commun. 2010, 46, 71247126, DOI: 10.1039/c0cc01880e
    13. 13
      (a) Sengupta, D.; Bhattacharjee, R.; Pramanick, R.; Rath, S. P.; Saha Chowdhury, N.; Datta, A.; Goswami, S. Exclusively Ligand-Mediated Catalytic Dehydrogenation of Alcohols. Inorg. Chem. 2016, 55, 96029610, DOI: 10.1021/acs.inorgchem.6b01310 .
      (b) Pramanick, R.; Bhattacharjee, R.; Sengupta, D.; Datta, A.; Goswami, S. An Azoaromatic Ligand as Four Electron Four Proton Reservoir: Catalytic Dehydrogenation of Alcohols by Its Zinc(II) Complex. Inorg. Chem. 2018, 57, 6816, DOI: 10.1021/acs.inorgchem.8b00034
    14. 14
      (a) Sinha, S.; Das, S.; Sikari, R.; Parua, S.; Brandaõ, P.; Demeshko, S.; Meyer, F.; Paul, N. D. Redox Noninnocent Azo-Aromatic Pincers and Their Iron Complexes. Isolation, Characterization, and Catalytic Alcohol Oxidation. Inorg. Chem. 2017, 56, 1408414100, DOI: 10.1021/acs.inorgchem.7b02238 .
      (b) Das, S.; Sinha, S.; Jash, U.; Sikari, R.; Saha, A.; Barman, S. K.; Brandão, P.; Paul, N. D. Redox-Induced Interconversion and Ligand-Centered Hemilability in Ni(II) Complexes of Redox-Noninnocent Azo-Aromatic Pincers. Inorg. Chem. 2018, 57, 58305841, DOI: 10.1021/acs.inorgchem.8b00231
    15. 15
      (a) Barham, J. P.; Coulthard, G.; Emery, K. J.; Doni, E.; Cumine, F.; Nocera, G.; John, M. P.; Berlouis, L. E. A.; McGuire, T.; Tuttle, T.; Murphy, J. A. KOtBu: A Privileged Reagent for Electron Transfer Reactions?. J. Am. Chem. Soc. 2016, 138, 74027410, DOI: 10.1021/jacs.6b03282 .
      (b) Yi, H.; Jutand, A.; Lei, A. Evidence for the Interaction Between tBuOK and 1,10-Phenanthroline to form the 1,10-Phenanthroline Radical Anion: a Key Step for the Activation of Aryl Bromides by Electron Transfer. Chem. Commun. 2015, 51, 545548, DOI: 10.1039/C4CC07299E .
      (c) Cuthbertson, J.; Gray, V. J.; Wilden, J. D. Observations on Transition Metal Free Biaryl Coupling: Potassium tert-Butoxide Alone Promotes the Reaction without Diamine or Phenanthroline Catalysts. Chem. Commun. 2014, 50, 25752578, DOI: 10.1039/C3CC49019J
    16. 16
      (a) Das, C.; Ghosh, A. K.; Hung, C.-H.; Lee, G.-H.; Peng, S.-M.; Goswami, S. Metal-Promoted Aromatic Ring Amination and Deamination Reactions at a Diazo Ligand Coordinated to Rhodium and Ruthenium. Inorg. Chem. 2002, 41, 71257135, DOI: 10.1021/ic020421c .
      (b) Das, C.; Saha, A.; Hung, C.-H.; Lee, G.-H.; Peng, S.-M.; Goswami, S. Ruthenium Complexes of 2-[(4-(Arylamino)phenyl)azo]pyridine Formed via Regioselective Phenyl Ring Amination of Coordinated 2-(Phenylazo)pyridine: Isolation of Products, X-ray Structure, and Redox and Optical Properties. Inorg. Chem. 2003, 42, 198204, DOI: 10.1021/ic0203724 .
      (c) Kamar, K. K.; Das, S.; Hung, C.-H.; Castiñeiras, A.; Kuz’min, M. D.; Rillo, K. C.; Bartolomé, J.; Goswami, S. Design and Synthesis of a New Binucleating Ligand via Cobalt-Promoted C–N Bond Fusion Reaction. Ligand Isolation and Its Coordination to Nickel, Palladium, and Platinum. Inorg. Chem. 2003, 42, 53675375, DOI: 10.1021/ic034313h
    17. 17

      The DFT barriers obtained at the BP86, def2-TZVP DFT-D3 level are rather low and do not explain the elevated temperatures needed in the experimental reactions. There can be several reasons for the need for elevated temperatures in the experimental catalytic reactions such as the presence of (lower energy) dormant species that were not explored computationally. The computational barriers might also be somewhat underestimated. Higher level calculations (using, e.g., meta-GGA functionals) could perhaps lead to somewhat higher barriers. However, exploring these possibilities is beyond the scope of the present paper.

    18. 18

      For nucleophiles where only one nitrogen center is available, the reaction will definitely go through the nitrogen that is bound to the iron center.

    19. 19
      Bruker SAINT-plus; Bruker AXS Inc.: Madison, WI, 2007.
    20. 20
      (a) Sheldrick, G. M. SHELXS-97, A Program for Crystal Structure Solution; University of Göttingen: Göttingen, Germany, 1997.
      (b) Sheldrick, G. M. SHELXL-97, a Program for Crystal Structure Refinement; University of Göttingen: Göttingen, Germany, 1997.
    21. 21
      Sheldrick, G. M. A short history of SHELX. Acta Crystallogr., Sect. A: Found. Crystallogr. 2008, A64, 112122, DOI: 10.1107/S0108767307043930
    22. 22
      Ahlrichs, R. Turbomole Version 6.5; Theoretical Chemistry Group, University of Karlsruhe, 2013.
    23. 23

      PQS version 2.4, 2001, Parallel Quantum Solutions, Fayettevile, Arkansas (USA); the Baker optimizer is available separately from PQS upon request:

      Baker, I. J. Comput. Chem. 1986, 7, 385, DOI: 10.1002/jcc.540070402
    24. 24
      Budzelaar, P. H. M. J. Comput. Chem. 2007, 28, 2226, DOI: 10.1002/jcc.20740
    25. 25
      (a) Becke, A. D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A: At., Mol., Opt. Phys. 1988, 38, 30983100, DOI: 10.1103/PhysRevA.38.3098 .
      (b) Perdew, J. P. Density-functional approximation for the correlation energy of the inhomogeneous electron gas. Phys. Rev. B: Condens. Matter Mater. Phys. 1986, 33, 88228824, DOI: 10.1103/PhysRevB.33.8822
    26. 26
      Sierka, M.; Hogekamp, A.; Ahlrichs, R. Fast evaluation of the Coulomb potential for electron densities using multipole accelerated resolution of identity approximation. J. Chem. Phys. 2003, 118, 91369148, DOI: 10.1063/1.1567253
    27. 27
      Schaefer, A.; Horn, H.; Ahlrichs, R. Fully optimized contracted Gaussian basis sets for atoms Li to Kr. J. Chem. Phys. 1992, 97, 25712577, DOI: 10.1063/1.463096
    28. 28
      Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132 (154104), 119, DOI: 10.1063/1.3382344
    29. 29
      Dzik, W. I.; Xu, X.; Zhang, X. P.; Reek, J. N. H.; de Bruin, B. ‘Carbene Radicals’ in CoII(por)-Catalyzed Olefin Cyclopropanation. J. Am. Chem. Soc. 2010, 132, 1089110902, DOI: 10.1021/ja103768r