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

[Hg{CH<sub>2</sub>C(O)Me}<sub>2</sub>] and K[PtCl<sub>3</sub>(C<sub>2</sub>H<sub>4</sub>)] react (2:1 molar ratio) to give K[Pt<sub>2</sub>{CH<sub>2</sub>C(O)Me}<sub>6</sub>(μ-Cl)<sub>3</sub>] (<b>1</b>·K) through the intermediate K[Pt{CH<sub>2</sub>C(O)Me}Cl<sub>2</sub>(η<sup>2</sup>-CH<sub>2</sub>CH<sub>2</sub>)] (<b>2</b>·K). The anionic complex <b>1</b> has been also obtained as the [K(18-C-6)]<sup>+</sup> salt (<b>1</b>·C) by reacting <b>1</b>·K with 18-crown-6, and <b>2</b> has been isolated as the Me<sub>4</sub>N salt (<b>2</b>·NMe<sub>4</sub>) by reacting [Hg{CH<sub>2</sub>C(O)Me}<sub>2</sub>] and K[PtCl<sub>3</sub>(C<sub>2</sub>H<sub>4</sub>)] (1:2) in the presence of an excess of (Me<sub>4</sub>N)Cl. The tris(acetonyl) Pt(IV) complexes <i>fac</i>-(PPN)<sub>2</sub>[Pt{CH<sub>2</sub>C(O)Me}<sub>3</sub>Cl<sub>3</sub>] (<b>3</b>), <i>fac</i>-[Pt{CH<sub>2</sub>C(O)Me}<sub>3</sub>(Cl)L<sub>2</sub>] (L = <sup>t</sup>BuNC (<b>4</b>), XyNC (<b>5</b>; Xy = C<sub>6</sub>H<sub>3</sub>Me<sub>2</sub>-2,6)), and <i>fac</i>-[Pt{CH<sub>2</sub>C(O)Me}<sub>3</sub>Cl(N∧N)] (N∧N = bpy (<b>6</b>), phen (<b>7</b>)) have been obtained by reacting <b>1</b>·K with (PPN)Cl, L, and N∧N, respectively, and <i>fac</i>-[Pt{CH<sub>2</sub>C(O)Me}<sub>3</sub>(CN<sup>t</sup>Bu)(bpy)]OTf (<b>8</b>) was obtained from <b>6</b>, TlTfO, and <sup>t</sup>BuNC. The mono(acetonyl) complex <i>mer</i>-[Pt{CH<sub>2</sub>C(O)Me}Cl<sub>3</sub>(bpy)] (<b>9</b>) and the bis(acetonyl) Pt(IV) derivatives [<i>OC</i>-6-13]-[Pt{CH<sub>2</sub>C(O)Me}<sub>2</sub>Cl<sub>2</sub>(bpy)] (<b>10</b>) and [<i>OC</i>-6-43]-[Pt{CH<sub>2</sub>C(O)Me}<sub>2</sub>(Me)I(bpy)] (<b>11</b>) have been obtained by reacting [Pt{CH<sub>2</sub>C(O)Me}Cl(bpy)] with PhICl<sub>2</sub> and by reacting [Pt{CH<sub>2</sub>C(O)Me}<sub>2</sub>(bpy)] with PhICl<sub>2</sub> and MeI, respectively. Room-temperature isomerization of <b>11</b> gives [<i>OC</i>-6-34]-[Pt{CH<sub>2</sub>C(O)Me}<sub>2</sub>(Me)I(bpy)] (<b>12</b>). The first mixed ketonylmetal complex, [<i>OC</i>-6-33]-[Pt{CH<sub>2</sub>C(O)Me}<sub>2</sub>{CH<sub>2</sub>C(O)Ph}Br(bpy)] (<b>13</b>), has been obtained by reacting [Pt{CH<sub>2</sub>C(O)Me}<sub>2</sub>(bpy)] with PhC(O)CH<sub>2</sub>Br. The crystal structures of <b>1</b>·C, <b>6</b>, <b>8</b>, and <b>9 </b>have been determined.