Binding and activation of halocarbons by iron(II) and ruthenium(II)

A series of cyclopentadienylruthenium(II) and -iron(II) complexes contain intact iodoalkanes, p-iodotoluene, or chelating (P, X) (o-halophenyl)diphenylphosphine (X = Cl, Br) ligands. The halocarbons coordinate via {sigma}-donation of a halogen lone pair and retain their carbon-halogen bonds. The complexes are synthesized from the halocarbon, metal halide, and silver(I) ion. Full characterization shows that they are Ru(II) complexes of intact halocarbons rather than Ru(IV) products of oxidative addition. The crystal and molecular structure of one such complex, (Cp(CO)(PPh{sub 3})Ru(IC{sub 6}H{sub 4}-p-CH{sub 3}))PF{sub 6}, is reported (P{bar 1}, a = 10.976 (3) {angstrom}, b = 11.329 (3) {angstrom}, c = 13.666 (4) {angstrom}, {beta} = 102.62 (3){degree}, Z = 2, R{sub 1} = 0.054, R{sub 2} = 0.065).