The First Family of Platinum(IV) Acetonyl Complexes. Mono-, Bis-, and Tris(acetonyl) Derivatives^†

[Hg{CH₂C(O)Me}₂] and K[PtCl₃(C₂H₄)] react (2:1 molar ratio) to give K[Pt₂{CH₂C(O)Me}₆(μ-Cl)₃] (1·K) through the intermediate K[Pt{CH₂C(O)Me}Cl₂(η²-CH₂CH₂)] (2·K). The anionic complex 1 has been also obtained as the [K(18-C-6)]⁺ salt (1·C) by reacting 1·K with 18-crown-6, and 2 has been isolated as the Me₄N salt (2·NMe₄) by reacting [Hg{CH₂C(O)Me}₂] and K[PtCl₃(C₂H₄)] (1:2) in the presence of an excess of (Me₄N)Cl. The tris(acetonyl) Pt(IV) complexes fac-(PPN)₂[Pt{CH₂C(O)Me}₃Cl₃] (3), fac-[Pt{CH₂C(O)Me}₃(Cl)L₂] (L = ^tBuNC (4), XyNC (5; Xy = C₆H₃Me₂-2,6)), and fac-[Pt{CH₂C(O)Me}₃Cl(N∧N)] (N∧N = bpy (6), phen (7)) have been obtained by reacting 1·K with (PPN)Cl, L, and N∧N, respectively, and fac-[Pt{CH₂C(O)Me}₃(CN^tBu)(bpy)]OTf (8) was obtained from 6, TlTfO, and ^tBuNC. The mono(acetonyl) complex mer-[Pt{CH₂C(O)Me}Cl₃(bpy)] (9) and the bis(acetonyl) Pt(IV) derivatives [OC-6-13]-[Pt{CH₂C(O)Me}₂Cl₂(bpy)] (10) and [OC-6-43]-[Pt{CH₂C(O)Me}₂(Me)I(bpy)] (11) have been obtained by reacting [Pt{CH₂C(O)Me}Cl(bpy)] with PhICl₂ and by reacting [Pt{CH₂C(O)Me}₂(bpy)] with PhICl₂ and MeI, respectively. Room-temperature isomerization of 11 gives [OC-6-34]-[Pt{CH₂C(O)Me}₂(Me)I(bpy)] (12). The first mixed ketonylmetal complex, [OC-6-33]-[Pt{CH₂C(O)Me}₂{CH₂C(O)Ph}Br(bpy)] (13), has been obtained by reacting [Pt{CH₂C(O)Me}₂(bpy)] with PhC(O)CH₂Br. The crystal structures of 1·C, 6, 8, and 9 have been determined.