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}Cl22-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(CNtBu)(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.