Dimethylplatinum(IV) chemistry: Stannyl, hydride, hydroxide, and aqua complexes

Abstract

The dimethylplatinum(II) complex [PtMe2(Me3TACN)] (Me3TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane) reacts easily with Me3SnCl, Me2SnCl2, or HX (X = CF3CO2, CF3SO3, BF4) to give the thermally stable cationic dimethyl platinum(IV) complexes [Pt(SnMe3)Me2(Me3TACN)]+, [Pt(SnMe2Cl)Me2(Me3TACN)]+, or [PtHMe2(Me3TACN)]+. The complexes [PtMe2(Me3TACN)] and [PtHMe2(Me3TACN)]+ are oxidized by moist air to give the hydroxo complex [PtMe2(OH)(Me3TACN)]+, which can then be protonated reversibly to form the aqua complex [PtMe2(OH2) (Me3TACN)]2+. The structures of the hydroxo complex [PtMe2(OH)(Me3TACN)]+, as both the BF[Formula: see text] or CF3SO[Formula: see text] salt, and of the mixed hydroxo, aqua complex [PtMe2(OH)(Me3TACN)][PtMe2(OH2)(Me3TACN)][BF4]3 have been determined and the complexes are shown to display interesting hydrogen bonding. Key words: platinum, oxidation, organometallic, tin, hydride.