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

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...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2023-06, Vol.52 (23), p.7828-7835
Main Authors: Giarrusso, Claudia P, Zeil, Daniel V, Blair, Victoria L
Format: Article
Language:English
Subjects:
Carbonyl compounds
Carbonyls
Catalysts
Hydroboration
Hydrosilylation
Ligands
Phosphines
Silver
Substrates
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Summary: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(PCy 3 )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 . Full characterisation and catalytic potential of two NHC-Ag( i )amide complexes with the influence of steric bulk of the NHC calculated via percent buried volume (% V Bur ), Solid-G ( G M ) and AtomAccess .
ISSN:1477-9226
1477-9234
DOI:10.1039/d3dt01042b