The synthesis, characterization and reactions of a binuclear tetramethylplatinum(IV) complex

Regioselective competition between the formation of seven-membered and five-membered cyclometalated platinacycles preceded by Csp2Csp3 reductive elimination

“…Both Pt-S-Me and Pt-N=CH coupling constants are also reduced compared to Pt(II) products thus supporting the assignment. The assigned stereochemistry of the six coordinate compounds has all three strong carbon donors fac as supported by previous work [66,68]. Furthermore, when Pt1-6 was refluxed in toluene, the products, Pt1-5/Pt1-7 were generated, supporting the notion that mechanistically the Pt(IV) is indeed an intermediate in the overall reaction that eventually results in the final Pt(II) complex.…”

A Tetramethylplatinum(IV) Complex with 1,1′‐Bis(diphenylphosphanyl)ferrocene Ligands: Reaction with Trifluoroacetic Acid

“…1,1′‐Bis(diphenylphosphanyl)ferrocene was purchased from Aldrich. The known precursor complexes cis , cis ‐[Me 2 Pt(μ‐SMe 2 ) 2 PtMe 2 ] ( 4 ),13 cis , cis ‐[Me 4 Pt(μ‐SMe 2 ) 2 PtMe 4 ] ( 1 ),1 [PtMe 4 (dppm)] ( 6 ),1 and [PtMe 4 (bpy)] ( 7 )1 were prepared according to literature methods. The stock solution of CF 3 CO 2 H was prepared by adding CF 3 CO 2 H (920 μL) to dichloromethane (10 mL).…”

“…Ever since the serendipitous synthesis of the binuclear tetramethylplatinum(IV) complex cis , cis ‐[Me 4 Pt(μ‐SMe 2 ) 2 PtMe 4 ] by the reaction of cis ‐[PtCl 2 (SMe 2 ) 2 ] with a mixture of MeLi/MeI,1 several related tetramethylplatinum(IV) complexes have been prepared by displacement of the labile SMe 2 ligands in this useful synthon with several phosphorus and nitrogen donor ligands, and some of their reactions have been studied 2. In these complexes, two Me groups are forced into the trans position to each other, and as a result of the high trans influence of the Me ligand, the Pt–Me bonds become rather weak, as suggested by a comparatively low Pt–C coupling constant;3 interesting reactions and properties are thus observed 2.…”

Kinetic study of the ligand substitution on the trimethylplatinum(iv) complexes with unidentate ligands

“…We have already studied kinetically reactions (1), (2), and (3) in this scheme [4,5]. It has been disclosed that reaction (1) proceeds with direct nucleophilic attack of dimethyl sulfide to the platinum(IV) dimer complex [3], while reaction (2) proceeds via a path with direct nucleophilic attack of NN to the bis(dimethyl sulfide)platinum(IV) complex in the case of NN ϭ 2,2Ј-bipyridine, and via both the direct path and a path with an intermediate of reduced coordination number in the case of NN ϭ 4,4Ј-dimethyl-2,2Ј-bipyridine [5]. On the other hand, reaction (3) has been shown to proceed with an mechanism S E2 [4].…”