A cooperative pathway for water activation using a bimetallic Pt0-CuI systemElectronic supplementary information (ESI) available. CCDC 1479263 and 1479264. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6dt03305a

A mixture of the platinum(0) complex [Pt(P t Bu 3 ) 2 ] and tetrakis(acetonitrile)copper( i ) hexafluorophosphate in acetone activated a water molecule and gave the hydride platinum( ii ) complex [PtH(CH 3 CN)(P t Bu 3 ) 2 ]PF 6 , 1 , and the hydroxide Cu( i ) species. The crystal structure of complex 1 was determined by X-ray crystallography, indicating a distorted square planar geometry around the platinum center. Although three possible mechanisms are proposed for this transformation, monitoring of the reaction using NMR spectroscopy at low temperature reveals that a cooperative pathway involving formation of a Pt 0 -Cu I dative bond complex is the most probable pathway. The hydride platinum complex 1 is stable in acidic and neutral conditions but undergoes intramolecular C-H activation in the presence of pyridine. Monitoring of the reaction using 1 H and 31 P NMR spectroscopy shows that a cyclometalation reaction of one of the phosphine ligands is followed by displacement of a second phosphine ligand by pyridine to give the cyclometalated platinum( ii ) complex, [Pt(κ 2 PC -P t Bu 2 CMe 2 CH 2 )(py) 2 ], 4 . The structure of 4 in solution and solid state phases was determined using NMR spectroscopy and X-ray crystallography, respectively. Cooperative activation of a water molecule with a bimetallic platinum(0)-copper( i ) system results in formation of copper( i ) hydroxide and a platinum hydride species. The latter is stable under acidic and neutral conditions but undergoes cyclometalation in the presence of pyridine.