Coinage metal amido and thiolate SNS complexes: consequences of catalyst speciation in Cu(I)-catalysed carbonyl hydroboration

Three new IPr-Ag- and -Au-SNS amido and thiolate complexes were synthesized and compared to their previously reported Cu analogues as carbonyl hydroboration catalysts (IPr = bis(2,6-diisopropylphenyl)imidazol-2-ylidene). Although these complexes showed no catalytic activity, treatment of the IPr-Ag-SNS amido complex with pinacolborane released the N-borylated ligand, S^MeN^BpinS^Me, (L¹-Bpin). This finding led us to reinvestigate the IPr-Cu-SNS amido precatalyst, revealing that immediate loss of L¹-Bpin converts our catalyst system to [CuH(IPr)]₂.