Reactivity of (NBu4)[Pt(C6F5)2(acac)] toward Electrophilic Metal Centers: Metal−Metal vs Metal−Cγ(acac) Bond Formation. Crystal Structure of [PtAg(C6F5)2(acac)(CH2Cl2)]2, a Complex Containing a μ2-acac-O,O‘ Bridging Ligand and a Coordinated Dichloromethane

Abstract

The reaction between (NBu4)[Pt(C6F5)2(acac)] and AgClO4 (1:1 molar ratio) in CH2Cl2 at room temperature gives the neutral tetranuclear complex [PtAg(C6F5)2(acac)]2 (1) in a good yield. The structure, which has been determined by single-crystal X-ray diffraction methods, shows two anionic fragments [Pt(C6F5)2(acac)]- linked by two Ag+ atoms, each silver center being bonded to a Pt atom of one fragment and to an oxygen atom of the acac ligand of the other fragment. Noteworthy structural features are the O-acac coordination of the silver atom (instead of the more usual Cγ coordination) and the unexpected presence of a dichloromethane molecule coordinated to the silver center. The reaction of 1 with tht (tht = SC4H8, tetrahydrothiophene) or PPh3 gives the dinuclear complexes [PtAg(C6F5)2(acac)(L)] (L = tht (2), PPh3 (3)) by cleavage of the O−Ag bond; alternatively, complexes 2 and 3 can be one-pot synthesized by reaction of (NBu4)[Pt(C6F5)2(acac)] and O3ClOAgL (L = tht, PPh3). Their structural characterizatio...