Au → M bonds promote catalytic alkyne hydrofunctionalisation.

The impact of metalloligands on Au catalysed alkyne hydrofunctionalisation is studied. Ambiphilic PMP-type ligands (M = Cu, Ag, Zn) stabilise Au → M bonds including unprecedented Au → Zn interactions. The Lewis acidity of Au increases in the order Cu < Ag < Zn promoting catalytic cycloisomerisation of propargylamide 14.

Evaluation of Pd→B Interactions in Diphosphinoborane Complexes and Impact on Inner-Sphere Reductive Elimination.

The dative Pd→B interaction in a series of DPB Pd and Pd complexes ( DPB =(o-PR C H ) BR', diphosphinoborane) was analyzed using XRD, B NMR spectroscopy and NBO/NLMO calculations. The borane acceptor discriminates between the oxidation state Pd and Pd , stabilizing the latter. Reaction of lithium amides with [( DPB )Pd (4-NO C H )I] chemoselectively yields the C-N coupling product.

Highly efficient palladium-catalysed carbon dioxide hydrosilylation employing PMP ligands.

A series of zero-valent palladium complexes featuring diphosphinometal ligands is reported. The metalloligand in the PMP-type framework (M = LiI, CuI, ZnII) acts as a weak to medium acceptor ligand for palladium. A Pd0→ZnII bond was observed in the solid state and further confirmed by NBO analysis.