Catalytic exploration of NHC-Ag(i)HMDS complexes for the hydroboration and hydrosilylation of carbonyl compounds

Claudia P. Giarrusso; Daniel V. Zeil; Victoria L. Blair

doi:10.1039/d3dt01042b

Catalytic exploration of NHC-Ag(i)HMDS complexes for the hydroboration and hydrosilylation of carbonyl compounds

Claudia P. Giarrusso, Daniel V. Zeil, Victoria L. Blair

School of Chemistry

Research output: Contribution to journal › Article › Research › peer-review

7 Citations (Scopus)

Abstract

The synthesis and full characterisation of two silver(i) amido complexes, stabilised by ancillary N-heterocyclic carbene (NHC) ligands is presented. The light stable complexes [Ag(IDipp)HMDS] 3 and [Ag(IAd)HMDS] 4 were explored as suitable pre-catalysts in the hydroboration and hydrosilylation of a range of carbonyl substrates, with complex 3 out-performing 4 and our previous phosphine-stabilised lead catalyst [Ag(PCy₃)HMDS] 5. This study highlights that changing the stabilising Lewis donor in the silver(i)amide system has an influence on catalytic efficiency. Finally, to shed light on the catalytic differences of pre-catalysts 3-5, we used a suite of programs to examine the influence of steric bulk on the Lewis donor ligand including percent buried volume (%V_Bur), Solid-G and AtomAccess which revealed the most sterically protected Ag(i) metal centre correlated to the most effective pre-catalyst 3.

Original language	English
Pages (from-to)	7828-7835
Number of pages	8
Journal	Dalton Transactions
Volume	52
Issue number	23
DOIs	https://doi.org/10.1039/d3dt01042b
Publication status	Published - 21 Jun 2023

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10.1039/d3dt01042b

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title = "Catalytic exploration of NHC-Ag(i)HMDS complexes for the hydroboration and hydrosilylation of carbonyl compounds",

abstract = "The synthesis and full characterisation of two silver(i) amido complexes, stabilised by ancillary N-heterocyclic carbene (NHC) ligands is presented. The light stable complexes [Ag(IDipp)HMDS] 3 and [Ag(IAd)HMDS] 4 were explored as suitable pre-catalysts in the hydroboration and hydrosilylation of a range of carbonyl substrates, with complex 3 out-performing 4 and our previous phosphine-stabilised lead catalyst [Ag(PCy3)HMDS] 5. This study highlights that changing the stabilising Lewis donor in the silver(i)amide system has an influence on catalytic efficiency. Finally, to shed light on the catalytic differences of pre-catalysts 3-5, we used a suite of programs to examine the influence of steric bulk on the Lewis donor ligand including percent buried volume (%VBur), Solid-G and AtomAccess which revealed the most sterically protected Ag(i) metal centre correlated to the most effective pre-catalyst 3.",

author = "Giarrusso, {Claudia P.} and Zeil, {Daniel V.} and Blair, {Victoria L.}",

note = "Funding Information: The authors acknowledge Dr Craig Forsyth, Dr Samantha Orr and Darcy Williamson for their assistance with crystallography and Dr Alasdair Mckay for his assistance with NMR spectroscopy, microanalysis and G-parameter calculations. The authors would also like to thank Dr Samantha Orr for her previous contribution to this study. The authors would finally like to thank Monash University and the Australian Research Council for financial support (FT200100918). Publisher Copyright: {\textcopyright} 2023 The Royal Society of Chemistry.",

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AU - Giarrusso, Claudia P.

AU - Zeil, Daniel V.

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N1 - Funding Information: The authors acknowledge Dr Craig Forsyth, Dr Samantha Orr and Darcy Williamson for their assistance with crystallography and Dr Alasdair Mckay for his assistance with NMR spectroscopy, microanalysis and G-parameter calculations. The authors would also like to thank Dr Samantha Orr for her previous contribution to this study. The authors would finally like to thank Monash University and the Australian Research Council for financial support (FT200100918). Publisher Copyright: © 2023 The Royal Society of Chemistry.

PY - 2023/6/21

Y1 - 2023/6/21

N2 - The synthesis and full characterisation of two silver(i) amido complexes, stabilised by ancillary N-heterocyclic carbene (NHC) ligands is presented. The light stable complexes [Ag(IDipp)HMDS] 3 and [Ag(IAd)HMDS] 4 were explored as suitable pre-catalysts in the hydroboration and hydrosilylation of a range of carbonyl substrates, with complex 3 out-performing 4 and our previous phosphine-stabilised lead catalyst [Ag(PCy3)HMDS] 5. This study highlights that changing the stabilising Lewis donor in the silver(i)amide system has an influence on catalytic efficiency. Finally, to shed light on the catalytic differences of pre-catalysts 3-5, we used a suite of programs to examine the influence of steric bulk on the Lewis donor ligand including percent buried volume (%VBur), Solid-G and AtomAccess which revealed the most sterically protected Ag(i) metal centre correlated to the most effective pre-catalyst 3.

AB - The synthesis and full characterisation of two silver(i) amido complexes, stabilised by ancillary N-heterocyclic carbene (NHC) ligands is presented. The light stable complexes [Ag(IDipp)HMDS] 3 and [Ag(IAd)HMDS] 4 were explored as suitable pre-catalysts in the hydroboration and hydrosilylation of a range of carbonyl substrates, with complex 3 out-performing 4 and our previous phosphine-stabilised lead catalyst [Ag(PCy3)HMDS] 5. This study highlights that changing the stabilising Lewis donor in the silver(i)amide system has an influence on catalytic efficiency. Finally, to shed light on the catalytic differences of pre-catalysts 3-5, we used a suite of programs to examine the influence of steric bulk on the Lewis donor ligand including percent buried volume (%VBur), Solid-G and AtomAccess which revealed the most sterically protected Ag(i) metal centre correlated to the most effective pre-catalyst 3.

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Catalytic exploration of NHC-Ag(i)HMDS complexes for the hydroboration and hydrosilylation of carbonyl compounds

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Synthesis, Synergy and Sustainability: Development of active-metal reagents

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Catalytic exploration of NHC-Ag(i)HMDS complexes for the hydroboration and hydrosilylation of carbonyl compounds

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Synthesis, Synergy and Sustainability: Development of active-metal reagents

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