Synthesis and reactivity of platinum-containing heterodinuclear complexes with methyl and 1,2-bis(diphenylphosphino)ethane ligands. X-Ray crystal structure of (dpe)MePt-FeCp(CO)2*THF

Article abstract of DOI:10.1016/0022-328X(94)80114-2

New-platinum-containing heterodinuclear complexes with methyl and 1,2-bis(diphenylphosphino)ethane (dpe) ligands have been prepared by metathetical reactions of PtMe(NO3)(dpe) with Na: MLn = MoCp(CO)3 (1); WCp(CO)3 (2); Mn(CO)5 (3); FeCp(CO)2 (4); Co(CO)4 (5).The molecular structure of (dpe)MePt-FeCp(CO)2*THF (4*THF) has been determined by X-ray crystallography: the geometry at Pt is square planar and the FeCp(CO)2 moiety has a piano-stool type structure.Thermolysis of 4 in C6D6 at 70 deg C for 2 h gives MeFeCp(CO)2 (8) in 30percent yield, but other dinuclear complexes are thermally stable under these conditions.Methyl migration to produce 8 was accelerated by the addition of electron-deficient olefins such as acrylonitrile and fumaronitrile.From the kinetic study, a mechanism involving two pathways is proposed: one is direct thermolysis from 4 to 8, while the other is the associative reductive elimination of 8 from the olefin-coordinated intermediate 9. Key words: Molybdenum; Platinum; Heterobimetallics; Iron; Tungsten; Manganese; Cobalt