Influence of <i>N</i>-Heterocyclic Carbene Steric Bulk on Selectivity in Nickel Catalyzed C–H Bond Silylation, Germylation, and Stannylation

Elsby, Matthew R.; Liu, Junyang; Zhu, Sha; Hu, Lingfei; Huang, Genping; Johnson, Samuel A.

doi:10.1021/acs.organomet.8b00786

Cited by 27 publications

(6 citation statements)

References 54 publications

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“…The combination of nickel with other "bulky yet flexible" ligands such as CAACs [88,89] and abnormal NHCs [90] also saw some success. Moreover, Montgomery [91], Louie [92] and Johnson [93] used this concept to further investigate and consequently advance the synthesis and catalytic application of styrene-based nickel complexes, thus building upon the work of Belderrain and Nicasio [94].…”

Section: Discussionmentioning

confidence: 99%

Bulky-Yet-Flexible Carbene Ligands and Their Use in Palladium Cross-Coupling

2019

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In recent years, several classes of new N-heterocyclic carbene (NHC) ligands were developed around the concept of “flexible steric bulk”. The steric hindrance of these ligands brings stability to the active species, while ligand flexibility still allows for the approach of the substrate. In this review, the synthesis of several types of new classes, such as IBiox, cyclic alkyl amino carbenes (CAAC), ITent, and IPr* are discussed, as well as how they move the state-of-the-art in palladium catalyzed cross-coupling forward.

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Section: Discussionmentioning

confidence: 99%

Bulky-Yet-Flexible Carbene Ligands and Their Use in Palladium Cross-Coupling

2019

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“…On the basis of kinetic studies and DFT computations, a mechanism of the deethenative metalation of arenes has been proposed (Scheme 222). 538 For all vinylmetalloids, the mechanism involves a similar sequence of steps starting with the oxidative addition of the C−H bond to the π-olefin complex (2), leading to a σ-alkyl stabilized by the interaction of hydrogen at position β with the metal center (3). As a result of β-ER 3 elimination, complex 4 is formed and undergoes reductive elimination of the carbon− ) has been reported by Jun.…”

Section: Stannylation Of C−h Bondsmentioning

confidence: 94%

Inorganometallics (Transition Metal–Metalloid Complexes) and Catalysis

et al. 2021

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While the formation and breaking of transition metal (TM)–carbon bonds plays a pivotal role in the catalysis of organic compounds, the reactivity of inorganometallic species, that is, those involving the transition metal (TM)–metalloid (E) bond, is of key importance in most conversions of metalloid derivatives catalyzed by TM complexes. This Review presents the background of inorganometallic catalysis and its development over the last 15 years. The results of mechanistic studies presented in the Review are related to the occurrence of TM–E and TM–H compounds as reactive intermediates in the catalytic transformations of selected metalloids (E = B, Si, Ge, Sn, As, Sb, or Te). The Review illustrates the significance of inorganometallics in catalysis of the following processes: addition of metalloid–hydrogen and metalloid–metalloid bonds to unsaturated compounds; activation and functionalization of C–H bonds and C–X bonds with hydrometalloids and bismetalloids; activation and functionalization of C–H bonds with vinylmetalloids, metalloid halides, and sulfonates; and dehydrocoupling of hydrometalloids. This first Review on inorganometallic catalysis sums up the developments in the catalytic methods for the synthesis of organometalloid compounds and their applications in advanced organic synthesis as a part of tandem reactions.

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“…All reactions and product manipulations were carried out in flame‐dried glassware under an inert atmosphere of argon using standard Schlenk‐line or glovebox techniques (maintained at <0.1 ppm H 2 O and <0.1 ppm O 2 ). Tetramethylcarbene (TMC) [21] , [{(IMes)Ni(CO)} 2 (μ 2 ,η 2 :η 2 ‐P 2 )] [13] and [(IMes)Ni(vtms) 2 ] [22] were prepared according to procedures previously reported in the chemical literature. All other chemicals were purchased from commercial suppliers and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

Diphosphorus Release and Heterocumulene Oligomerisation by Nickel Complexes

Hierlmeier

Wolf

2022

Eur J Inorg Chem

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The generation of diphosphorus molecules P 2 under mild conditions in solution is a useful strategy to generate diphosphines via [4 + 2] cycloadditions. We recently described the release of P 2 units from the nickel butterfly complex [{(IMes)Ni(CO)} 2 (μ 2 ,η 2 :η 2 -P 2 )](IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) upon addition of CO gas. Herein, we developed an alternative protocol for the same process using heterocumulenes. In addition to formation of P 4 (the dimerisation product of P 2 ), the reactions afford nickel com-plexes of novel pincer-type ligands. Aryl isothiocyanates undergo a trimerisation within the coordination sphere of nickel and afford square planar nickel complexes with SÀ CÀ S pincer-ligand frameworks. Carbon disulfide coordinates to the [(IMes)Ni]fragment in an η 2 -fashion, affording a dinuclear complex. Similar products are formed when the N-heterocyclic carbene nickel(0) complex [(IMes)Ni(vtms) 2 ] is used as a precursor (vtms = vinyltrimethylsilane).

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Influence of N-Heterocyclic Carbene Steric Bulk on Selectivity in Nickel Catalyzed C–H Bond Silylation, Germylation, and Stannylation

Cited by 27 publications

References 54 publications

Bulky-Yet-Flexible Carbene Ligands and Their Use in Palladium Cross-Coupling

Bulky-Yet-Flexible Carbene Ligands and Their Use in Palladium Cross-Coupling

Inorganometallics (Transition Metal–Metalloid Complexes) and Catalysis

Diphosphorus Release and Heterocumulene Oligomerisation by Nickel Complexes

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