Structure and reactivity of gold cluster protected by triphosphine ligands: DFT study

The structure and reactivity of rhombic Au 4 cluster protected by bis(dimethylphosphinomethyl) and phenylacetylide ligands towards CO and O 2 were studied in scalar-relativistic DFT/PBE approach. The cluster is inert to noticeable CO binding or activation, while it reacts with O 2 and forms peroxide [O 2 Au 4 ( dmmp ) 2 (С ≡ CCH 3 ) 2 ] 2+ complexes. The CO oxidation on the cluster was simulated. According to the calculation and analysis of different pathways of reaction, the Au–P fragments of the cluster are the most probable active sites. The protected gold clusters are predicted to be promising heterogeneous catalysts in CO oxidation.