The C-H activation of toluene and p-xylene at cationic Pt(II) diimine complexes (N-N)Pt(CH(3))(H(2)O)(+)BF(4)(-) (N-N = Ar-N=CMe-CMe=N-Ar; 1(BF(4)(-)), N(f)-N(f), Ar = 3,5-(CF(3))(2)C(6)H(3)); 2(BF(4)(-)), N'-N', Ar = 2,6-(CH(3))(2)C(6)H(3)) has been investigated. The reactions were performed at ambient temperature in 2,2,2-trifluoroethanol (TFE), and after complete conversion of the starting material to mixtures of Pt-aryl/Pt-benzyl complexes and methane, acetonitrile was added to trap the products as more stable acetonitrile adducts. In the reactions with toluene, the relative amounts of products resulting from aromatic C-H activation were found to decrease in the order (N-N)Pt(m-tolyl)(NCMe)(+) > (N-N)Pt(p-tolyl)(NCMe)(+) > (N-N)Pt(o-tolyl)(NCMe)(+) for both 1 and 2. Unlike the reaction at 1, significant amounts of the benzylic activation product (N'-N')Pt(benzyl)(NCMe)(+) were concurrently formed in the C-H activation of toluene at 2. The C-H activation of p-xylene revealed an even more remarkable difference between 1 and 2. Here, the product ratios of (N-N)Pt(xylyl)(NCMe)(+) and (N-N)Pt(p-methylbenzyl)(NCMe)(+) were found to be 90:10 and 7:93 for reactions at 1 and 2, respectively. The elimination of toluene from (N(f)-N(f))Pt(Tol)(2) species (3a-c; a, Tol = o-tolyl; b, Tol = m-tolyl; c, Tol = p-tolyl) after protonolysis with 1 equiv of HBF(4) was investigated. Most notably, protonation in neat TFE followed by addition of acetonitrile gave a 77:23 mixture of (N(f)-N(f))Pt(m-tolyl)(NCMe)(+) (4b) and (N(f)-N(f))Pt(p-tolyl)(NCMe)(+) (4c) from all three isomeric bis(tolyl) complexes 3a-c. The presence of acetonitrile during the protonation reactions resulted in considerably less isomerization. This behavior is explained by an associative mechanism for the product-determining displacement of toluene by the solvent. For the C-H activation reactions, our findings suggest the existence of a dynamic equilibrium between the isomeric intermediates (N-N)Pt(aryl)(CH(4))(+) (aryl = tolyl/benzyl from 1; xylyl/p-methylbenzyl from 2). The observed selectivities might then be explained by steric and electronic effects in the pentacoordinate transition-state structures for the solvent-induced associative elimination of methane from these intermediates.

The redox chemistry of the series of Pt(II) diimine complexes L2PtMe2 (1; L2 = Ar−NCRCRN−Ar, where Ar/R = 4-MeC6H4/H (a), 4-MeOC6H4/H (b), 4-MeC6H4/Me (c), 4-MeOC6H4/Me (d)), with particular emphasis on the oxidation processes, has been studied in detail. As seen by cyclic voltammetry, 1a−d undergo two successive, reversible one-electron reductions at the diimine ligands and an irreversible, metal-centered one-electron oxidation. The oxidation of 1b has been investigated in some detail. Chemical oxidation of 1b with Cp2Fe+PF6 - in acetonitrile yields a near 1:1 ratio of the corresponding Pt(II) and Pt(IV) cations L2Pt(NCMe)Me+ (2b) and fac-L2Pt(NCMe)Me3 + (3b). Controlled-potential electrolysis of 1b yields mixtures of 2b and 3b in a 1:1 ratio, as well as the cis,cis (4b) and one cis,trans (5b) isomer of the dicationic Pt(IV) complexes L2Pt(NCMe)2Me2 2+. The percentage of the dications 4b and 5b depended on the electrode potential. A mechanism involving methyl group transfer between two transient Pt(III) intermediates L2PtMe2 •+ is proposed to account for the generation of 2b and 3b, whereas further oxidation of the Pt(III) species at the electrode eventually provides 4b and 5b. The X-ray crystal structures of 1b and 3b(OTf-) have been determined. All Pt−Me bond distances in these two species are essentially identical, averaging 2.057(1) Å.