Oxidation of Half-Lantern Pt2(II,II) Compounds by Halocarbons. Evidence of Dioxygen Insertion into a Pt(III)-CH3 Bond

The half-lantern compound [{Pt(bzq)(μ-N^S)}2] (1) [bzq = benzo[h]quinoline, HN^S = 2-mercaptopyrimidine (C4H3N2HS)] reacts with CH3I and haloforms CHX3 (X = Cl, Br, I) to give the corresponding oxidized diplatinum(III) derivatives [{Pt(bzq)(μ-N^S)X}2] (X = Cl 2a, Br 2b, I 2c). These compounds exhibit half-lantern structures with short intermetallic distances (∼2.6 Å) due to Pt-Pt bond formation. The halogen abstraction mechanisms from the halocarbon molecules by the Pt2(II,II) compound 1 were investigated. NMR spectroscopic evidence using labeled reagents support that in the case of (13)CH3I the reaction initiates with an oxidative addition through an SN2 mechanism giving rise to the intermediate species [I(bzq)Pt(μ-N^S)2Pt(bzq)((13)CH3)}]. However, with haloforms the reactions proceed through a radical-like mechanism, thermally (CHBr3, CHI3) or photochemically (CHCl3) activated, giving rise to mixtures of species [X(bzq)Pt(μ-N^S)2Pt(bzq)R] (3a-c) and [X(bzq)Pt(μ-N^S)2Pt(bzq)X] (2a-c). In these cases the presence of O2 favors the formation of species 2 over 3. Transformation of 3 into 2 was possible upon irradiation with UV light. In the case of [I(bzq)Pt(μ-N^S)2Pt(bzq)((13)CH3)}] (3d), in the presence of O2 the formation of the unusual methylperoxo derivative [I(bzq)Pt(μ-N^S)2Pt(bzq)(O-O(13)CH3)}] (4d) was detected, which in the presence of (13)CH3I rendered the final product [{Pt(bzq)(μ-N^S)I}2] (2c) and (13)CH3OH.