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Catalytic reduction of aryl trialkylammonium salts to aryl silanes and arenes.

ABSTRACT: A new approach for the reduction of aryl ammonium salts to arenes or aryl silanes using nickel catalysis is reported. This method displays excellent ligand-controlled selectivity based on the N-heterocyclic carbene (NHC) ligand employed. Utilizing a large NHC in non-polar solvents generates aryl silanes, while small NHCs in polar solvents promote reduction to arenes. Several classes of aryl silanes can be accessed from simple aniline building blocks, including those useful for cross-couplings, oxidations, and halogenations. The reaction conditions are mild, functional group tolerant, and provide efficient access to a variety of benzene derivatives.

SUBMITTER: Rand AW

PROVIDER: S-EPMC6540906 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

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Catalytic reduction of aryl trialkylammonium salts to aryl silanes and arenes.

Rand Alexander W AW Montgomery John J

Chemical science 20190426 20

A new approach for the reduction of aryl ammonium salts to arenes or aryl silanes using nickel catalysis is reported. This method displays excellent ligand-controlled selectivity based on the N-heterocyclic carbene (NHC) ligand employed. Utilizing a large NHC in non-polar solvents generates aryl silanes, while small NHCs in polar solvents promote reduction to arenes. Several classes of aryl silanes can be accessed from simple aniline building blocks, including those useful for cross-couplings, o ...[more]

PMID: 31191891

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Project description:Using density functional theory computations, we investigated in detail the underlying reaction mechanism and crucial intermediates present during the reduction of carbon dioxide to methane with silanes, catalyzed by the cationic Ir-pincer complex ((POCOP)Ir(H)(acetone)+, POCOP = 2,6-bis(dibutylphosphinito)phenyl). Our study postulates a plausible catalytic cycle, which involves four stages, by sequentially transferring silane hydrogen to the CO2 molecule to give silylformate, bis(silyl)acetal, methoxysilane and the final product, methane. The first stage of reducing carbon dioxide to silylformate is the rate-determining step in the overall conversion, which occurs via the direct dissociation of the silane Si-H bond to the C[double bond, length as m-dash]O bond of a weakly coordinated Ir-CO2 moiety, with a free energy barrier of 29.5 kcal mol-1. The ionic SN2 outer-sphere pathway in which the CO2 molecule nucleophilically attacks at the η1-silane iridium complex to cleave the η1-Si-H bond, followed by the hydride transferring from iridium dihydride [(POCOP)IrH2] to the cation [O[double bond, length as m-dash]C-OSiMe3]+, is a slightly less favorable pathway, with a free energy barrier of 33.0 kcal mol-1 in solvent. The subsequent three reducing steps follow similar pathways: the ionic SN2 outer-sphere process with silylformate, bis(silyl)acetal and methoxysilane substrates nucleophilically attacking the η1-silane iridium complex to give the ion pairs [(POCOP)IrH2] [HC(OSiMe3)2]+, [(POCOP)IrH2] [CH2(OSiMe3)2(SiMe3)]+, and [(POCOP)IrH2] [CH3O(SiMe3)2]+, respectively, followed by the hydride transfer process. The rate-limiting steps of the three reducing stages are calculated to possess free energy barriers of 12.2, 16.4 and 22.9 kcal mol-1, respectively. Furthermore, our study indicates that the natural iridium dihydride [(POCOP)IrH2] generated along the ionic SN2 outer-sphere pathway could greatly facilitate the silylation of CO2, with a potential energy barrier calculated at a low value of 16.7 kcal mol-1.

Dataset Information

Catalytic reduction of aryl trialkylammonium salts to aryl silanes and arenes.

Publications

Catalytic reduction of aryl trialkylammonium salts to aryl silanes and arenes.

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