SYNTHESIS AND CHARACTERIZATION OF NEW DITHIOFORMATO, THIOFORMAMIDO, FORMAMIDO AND DI-P-TOLYLFORMAMIDINATO COMPLEXES OF RUTHENIUM AND OSMIUM

The synthesis of [M(S2CH)P4]+, 1, [M{RNC(H)S}P4]+, 2 and [M{R1NC(H)NR1 }P4]+, 3 [M = Ru, Os; P = P(OMe)3, a, P(OEt)3, b, PPh(OEt)2, c; R = p - MeC6H4, Et; R-1 = p - MeC6H4] derivatives has been achieved by react ing non-classical hydrides [MH(eta2-H2)P4]+ with heteroallenes CS2, RN CS and R1NCNR1, respectively. The related formamido complexes [M{PhNC( H)O}P4]CF3SO3, 4, were prepared by sequential reaction of dihydrides M H2P4 with methyl triflate and phenyl isocyanate. Reactivity studies wi th CO and p-tolyl isocyanide are described and lead to the synthesis o f monosubstituted species of the type ]Ru{RNC(H)S}(CO)P3]+, [Ru{R1NC(H )NR1}(CO)P3]+, [Ru(RNC(H)S)(ArNC){PPh(OEt)2}3]+ and [Ru{R1NC(H)NR1}(Ar NC){PPh(OEt)2}3]+ (Ar = p-MeC6H4) and to tris-isocyanide [Ru(ArNC)3{P( OEt)3}3]2+ derivatives. Characterization of all complexes by R and H-1 -, P-31- and C-13 NMR spectra is also discussed.