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Chlorocarbon solvents (solv=CH(2)Cl(2), CHCl(3)) are suggested to play an active role in the oxidative addition of halogens, X(2) (X=Cl, Br, I), to homoleptic d(8) perfluoromethyl and -phenyl platinum(II) species [Pt(R(F))(4)](2-) (R(F)=CF(3), C(6)F(5)). The perfluoromethyl group, CF(3), has been found to be considerably less prone to undergo reductive elimination processes, and is, therefore, more suitable for stabilizing organoplatinum(IV) derivatives (see scheme).The equilibrium geometries of the homoleptic perfluorinated organoplatinate(II) anions [Pt(CF(3))(4)](2-) and [Pt(C(6)F(5))(4)](2-) have been computed at the B3P86/LANL2DZ level of theory. Remarkably good agreement with the experimentally determined structures has been obtained by X-ray diffraction methods. The reactivity of [NBu(4)](2)[Pt(CF(3))(4)] (1) towards halogens (Cl(2), Br(2), and I(2)) has been investigated by using a combined experimental and theoretical approach. The perfluoromethyl derivative 1 has been found to undergo clean oxidative addition of the three halogens under investigation, giving rise to [NBu(4)](2)[trans-Pt(CF(3))(4)X(2)] (X=Cl (7), Br (10), I (13)) in a quantitative and stereoselective way. In the low-temperature reaction of the perfluorophenyl derivative [NBu(4)](2)[Pt(C(6)F(5))(4)] (3) with Cl(2) or Br(2), the corresponding oxidative-addition products [NBu(4)](2)[trans-Pt(C(6)F(5))(4)X(2)] (X=Cl (14), Br (15)) can also be obtained. In the case in which X=Br and working in CHCl(3) at -55 degrees C, it has been possible to detect the formation of an intermediate species to which we assign the formula [trans-Pt(C(6)F(5))(4)Br(ClCHCl(2))](-) (16). The solvento complex 16 is thermally unstable and prone to undergo reductive elimination of C(6)F(5)--C(6)F(5). In the presence of PhCN, complex [NBu(4)][trans-Pt(C(6)F(5))(4)Br(NCPh)] (17) was isolated and structurally characterized. The reaction of 3 with I(2) gave no organoplatinum(IV) compound. Our comparative study reveals that the CF(3) group is especially suited to stabilize organometallic compounds in high oxidation states. This ability can be attributed to a combination of factors: its hardness, its high group electronegativity, its small size, and its reluctance to undergo reductive elimination processes.

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The oxidative addition of Br2 to [NBu4]2[Pt(C6F5)4] followed by halide extraction with AgClO4 in the presence of CO gave [NBu4][trans-PtIV(C6F5)4Br(CO)], the first Pt(IV) carbonyl derivative to be structurally characterized. It is demonstrated that the previously reported [NEt4][PtBr3H2(CO)] complex is, in fact, the Pt(II) derivative [NEt4][PtBr3(CO)].