title: A cooperative pathway for water activation using a bimetallic Pt0-CuIsystem.
abstract: A mixture of the platinum(0) complex [Pt(PtBu3)2] and tetrakis(acetonitrile)copper(i) hexafluorophosphate in acetone activated a water molecule and gave the hydride platinum(ii) complex [PtH(CH3CN)(PtBu3)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 Pt0-CuIdative 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 using1H and31P 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(κ2PC-PtBu2CMe2CH2)(py)2], 4. The structure of 4 in solution and solid state phases was determined using NMR spectroscopy and X-ray crystallography, respectively.
authors.affiliation: Chemistry Department, Sharif University of Technology, P.O. Box 11155-3516, Tehran, Iran. sjamali@sharif.ir.
authors.forename: S
authors.initials: S
authors.lastname: Jamali
authors.forename: S
authors.initials: S
authors.lastname: Abedanzadeh
authors.forename: N K
authors.initials: NK
authors.lastname: Khaledi
authors.forename: H
authors.initials: H
authors.lastname: Samouei
authors.forename: Z
authors.initials: Z
authors.lastname: Hendi
authors.forename: S
authors.initials: S
authors.lastname: Zacchini
authors.forename: R
authors.initials: R
authors.lastname: Kia
authors.forename: H R
authors.initials: HR
authors.lastname: Shahsavari