A cooperative pathway for water activation using a bimetallic Pt-0-Cu-I system

作者：Jamali S^*; Abedanzadeh S; Khaledi N K; Samouei H; Hendi Z; Zacchini S; Kia R; Shahsavari H R

来源：Dalton Transactions, 2016, 45(44): 17644-17651.

DOI：10.1039/c6dt03305a

A mixture of the platinum(0) complex [Pt((PBu3)-Bu-t)(2)] and tetrakis(acetonitrile) copper(I) hexafluorophosphate in acetone activated a water molecule and gave the hydride platinum(II) complex [PtH(CH3CN)((PBu3)-Bu-t)(2)] PF6, 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 H-1 and P-31 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(kappa(2)(PC)-(PBu2CMe2CH2)-Bu-t)(py)(2)], 4. The structure of 4 in solution and solid state phases was determined using NMR spectroscopy and X-ray crystallography, respectively.

• 出版日期2016