Ni/NHC catalysis in C–H functionalization using air-tolerant nickelocene and sodium formate for <i>in situ</i> catalyst generation

Khazipov, Oleg V.; Shepelenko, Konstantin E.; Pasyukov, Dmitry V.; Chesnokov, V. V.; Soliev, Safarmurod B.; Чернышев, В. М.; Ananikov, Valentine P.

doi:10.1039/d1qo00309g

Cited by 24 publications

(22 citation statements)

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“…These complexes contain NHC ligands of various steric bulkiness, different saturations of the (benz)imidazole core, and various coligands. Complexes 1d – f were prepared for the first time by palladation of the corresponding imidazolinium salts, and complexes 1a – c , 1g – l , and 2a – e were obtained by previously described procedures. − …”

Section: Results and Discussionmentioning

confidence: 99%

Discovery of the N–NHC Coupling Process under the Conditions of Pd/NHC- and Ni/NHC-Catalyzed Buchwald–Hartwig Amination

et al. 2022

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Complexes of palladium and nickel with Nheterocyclic carbene ligands (M/NHC, M = Pd, Ni) are widely used as effective catalysts for various amination reactions. A previously unaddressed transformation of M/NHC complexes under typical conditions of the Buchwald−Hartwig amination is disclosed. M II /NHC complexes react with primary aromatic and aliphatic amines in the presence of strong bases to give azol-2(5)imines and M(0) species via a reductive elimination of NHC and azanide (N-deprotonated amine) ligands. Depending on the structures of the NHC and azanide, the N−NHC coupling can make a significant contribution to the M/NHC catalyst decomposition in the Buchwald−Hartwig and other amination reactions conducted in the presence of strong bases. The discovery of the N−NHC coupling reaction has been shown to be critically influenced by the steric bulkiness of N-substituents on the NHC ligand. The high steric bulkiness of the NHC is an important factor in suppressing the N−NHC coupling deactivation pathway.

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Section: Results and Discussionmentioning

confidence: 99%

Discovery of the N–NHC Coupling Process under the Conditions of Pd/NHC- and Ni/NHC-Catalyzed Buchwald–Hartwig Amination

et al. 2022

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“…Our comprehensive search using the Cambridge Crystallographic Data Centre database has led to the conclusion that the AgX It should be noticed that the tetrahydropyrimidin-2ylidene silver(I) complex 84 with less bulky N-isopropyl substituent in the carbene structure has reacted with PdCl 2 (CH 3 CN) 2 under the same conditions with the formation of neutral complex 86, structure of which has been confirmed by the X-ray diffraction analysis data [142]. As per the 13 С NMR spectroscopy data, the PdC carbene atom gives two signals, at 192.1 and 192.5 ppm. Probably, the presence of two signals can be explained by the cis-trans isomerism.…”

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confidence: 83%

“…Three bridging chlorine atoms have been found in the anion of both compounds, and compound 73 has revealed the noncovalent heterohalogen interaction of the terminal chlorine atoms of the [{(η 5 -C 5 H 5 )ZrCl} 2 (η 2 -Cl) 3 ]anion and the bromine in the para-position of the N-aryl substituent of the complex cation. The carbene carbon atom C-Ag in compound 72 has not been manifested in the 13 С{ 1 H} NMR spectrum (100 MHz, DMSO-d 6 ), evidencing fast ligands exchange in the solution. Compound 73 has been insoluble in standard deuterated solvents, being rapidly decomposed upon dissolution in DMSO-d 6 .…”

Section: Transformation Of Heteroleptic N-heterocyclic Carbene Complexes (Nhc)m C X Into Cationic Homoleptic Complexes [(Nhc) 2 M C ] + Umentioning

confidence: 98%

“…Owing to the pronounced ability to stabilize uncommon compounds of metals in diverse oxidation states, diaminocarbenes (Scheme 1) are key ligands, and their complexes with different transition metals have been applied in biomedicine [1][2][3][4][5][6][7][8][9][10], as catalysts in wide range of organic reactions [11][12][13][14][15][16][17][18][19][20][21][22], and in the development of functional and luminescent materials [23][24][25].…”

Section: Introductionmentioning

confidence: 99%

“…In the later paper [144], the author has suggested a similar transformation of the N-mesityl-functionalized complex 83 containing a bulky biscycloheptene substituent in the tetrahydropyrimidine ring (Scheme 28, R 1 = Mes, R 2 = Y), yielding compound 85 Y , however, the suggested structure has not been confirmed by X-ray diffraction analysis. At the same time, Herrmann has analyzed the X-ray diffraction analysis, mass spectrometry, 13 С NMR spectroscopy, and color data for the compounds mentioned in the study by Buchmeiser and has reliably concluded that the structure of compound 85 in fact corresponds to the homoleptic biscarbene silver(I) complex analogous to complex 81.…”

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Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

Mikhaylov

Балова

2021

Russ J Gen Chem

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The carbene transfer from N-heterocyclic carbene complexes of Group 11 metals (NHC-M C ) (especially silver and copper) to other metals is considered a convenient and universal, sometimes having no alternative, method for the synthesis of a wide range of important N-heterocyclic carbene complexes of transition metals. As the number of successful examples of transmetalation with the formation of the target product has increased, the data were accumulated on alternative or unexpected results of the interaction of NHC-M C complexes with compounds of other metals. This review considers the examples of NHC-M C reactions with compounds of other metals which proceed with a change in the metals oxidation state, conversion of (NHC)M C X into cationic homoleptic [(NHC) 2 M C ] + forms, transmetalation retaining the other metal in the coordination sphere of the product, or formation of heterometallic adducts preserving the M C -C carbene bond, rather than these occurring according to the standard reaction pathway. Unusual "reverse" carbene transfer reactions have been considered separately. The review material reveals a promising new synthetic potential of NHC-M C in the reactions with other metals and discusses the possible mechanisms and driving forces of such transformations. The most important aspects of the application of the obtained products, primarily in various catalytic processes, have been considered as well.

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Recent advances in catalytic and electrocatalytic applications of half‐sandwich nickel(0/II) N–heterocyclic carbene complexes

Budagumpi,

Narayana,

Keri

et al. 2023

Applied Organom Chemis

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Diverse structural and catalytic features of half‐sandwich nickel N–heterocyclic carbene (NHC) complexes provide an encouraging platform not only to address the drawbacks of other group X (palladium and platinum) metal NHC catalysts but also to bring about their superior performance. The chemistry of nickel NHC complexes has gained substantial interest from the organometallic community owing to their remarkable stability to air and moisture, easier preparation protocols, and availability of wide scope for structural fine tuning in order to achieve targeted applications. The recent progress in the field of half‐sandwich nickel(0/II) NHC complexes is covered in this review article with a special emphasis on the different synthetic strategies employed, structural characterization including spectral and X‐ray diffraction techniques, and surface morphology of the films of complexes. Both, homogeneous and electrocatalytic applications of half‐sandwich nickel NHC complexes are discussed with respect to their potential in various C–C and C–S bond constructions, targeted C–H bond activations, reductions using silylating agents, electrocatalytic glucose sensing, and electrocatalytic hydrogen evolution reactions. Donor functionalized complexes displayed improved catalytic potential in several C–C and C–S coupling reactions over non–functionalized counterparts. Overall, this assessment, from a comprehensive standpoint, affords evidence that is advantageous in the design of novel NHC ligands to access targeted half‐sandwich nickel(0/II) NHC complexes encompassing potential homogeneous catalytic and electrocatalytic applications.

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Ni/NHC catalysis in C–H functionalization using air-tolerant nickelocene and sodium formate for in situ catalyst generation

Abstract: A facile method for Ni/NHC catalyzed C–H alkylation and alkenylation of heteroarenes with alkenes and internal alkynes using air-tolerant nickelocene, sodium formate and NHC·HCl salts for in situ catalyst generation has been developed.

Cited by 24 publications

References 92 publications

Discovery of the N–NHC Coupling Process under the Conditions of Pd/NHC- and Ni/NHC-Catalyzed Buchwald–Hartwig Amination

Discovery of the N–NHC Coupling Process under the Conditions of Pd/NHC- and Ni/NHC-Catalyzed Buchwald–Hartwig Amination

Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

Recent advances in catalytic and electrocatalytic applications of half‐sandwich nickel(0/II) N–heterocyclic carbene complexes

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