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(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.二(丙酮基)合汞(II) ([Hg{CH2C(O)Me}2])与三氯(乙烯)合铂酸钾(K[PtCl3(C2H4)])以2:1的摩尔比反应，经由中间体二氯(η2-乙烯)(丙酮基)合铂酸钾(K[Pt{CH2C(O)Me}Cl2(η2-CH2=CH2)]，即2·K)，得到三(丙酮基)三(μ-氯)合二铂酸钾(K[Pt2{CH2C(O)Me}6(μ-Cl)3]，即1·K)。将1·K与18-冠-6(18-C-6)反应，可得到[K(18-C-6)]+盐形式的阴离子配合物1·C；在过量四甲基氯化铵((Me4N)Cl)存在下，使[Hg{CH2C(O)Me}2]与K[PtCl3(C2H4)]以1:2的摩尔比反应，可分离得到四甲基铵盐形式的2·NMe4。三(丙酮基)铂(IV)配合物面式(fac-)(PPN)2[Pt{CH2C(O)Me}3Cl3] (3)、fac-[Pt{CH2C(O)Me}3(Cl)L2]（L = 叔丁基异腈(tBuNC) (4)、2,6-二甲基苯基异腈(XyNC) (5；Xy = C6H3Me2-2,6)）以及fac-[Pt{CH2C(O)Me}3Cl(N∧N)]（N∧N = 联吡啶(bpy) (6)、邻菲啰啉(phen) (7)），可分别通过1·K与(PPN)Cl、配体L以及双齿氮配体N∧N反应制得；而fac-[Pt{CH2C(O)Me}3(CNtBu)(bpy)]三氟甲磺酸盐(OTf) (8)则由6、三氟甲磺酸铊(TlTfO)与叔丁基异腈反应得到。单(丙酮基)配合物经式(mer-)[Pt{CH2C(O)Me}Cl3(bpy)] (9)以及双(丙酮基)铂(IV)衍生物[OC-6-13]-[Pt{CH2C(O)Me}2Cl2(bpy)] (10)和[OC-6-43]-[Pt{CH2C(O)Me}2(Me)I(bpy)] (11)，可分别通过[Pt{CH2C(O)Me}Cl(bpy)]与二氯碘苯(PhICl2)反应，以及[Pt{CH2C(O)Me}2(bpy)]分别与PhICl2和碘甲烷(MeI)反应得到。配合物11在室温下发生异构化，得到[OC-6-34]-[Pt{CH2C(O)Me}2(Me)I(bpy)] (12)。首例混合酮基金属配合物[OC-6-33]-[Pt{CH2C(O)Me}2{CH2C(O)Ph}Br(bpy)] (13)，可通过[Pt{CH2C(O)Me}2(bpy)]与溴代苯乙酮(PhC(O)CH2Br)反应制得。已测定配合物1·C、6、8和9的晶体结构。