Dithiocarboxylate complexes of ruthenium(II) and osmium(II).

The ruthenium(II) complexes Ru(R)(κ(2)-S(2)C·IPr)(CO)(PPh(3))(2) (R = CH=CHBu(t), CH=CHC(6)H(4)Me-4, C(C≡CPh)=CHPh) are formed on reaction of IPr·CS(2) with [Ru(R)Cl(CO)(BTD)(PPh(3))(2)] (BTD = 2,1,3-benzothiadiazole) or [Ru(C(C≡CPh)=CHPh)Cl(CO)(PPh(3))(2)] in the presence of ammonium hexafluorophosphate. Similarly, the complexes Ru(CH=CHC(6)H(4)Me-4)(κ(2)-S(2)C·ICy)(CO)(PPh(3))(2) and Ru(C(C≡CPh)=CHPh)(κ(2)-S(2)C·ICy)(CO)(PPh(3))(2) are formed in the same manner when ICy·CS(2) is employed. The ligand IMes·CS(2) reacts with [Ru(R)Cl(CO)(BTD)(PPh(3))(2)] to form the compounds Ru(R)(κ(2)-S(2)C·IMes)(CO)(PPh(3))(2) (R = CH=CHBu(t), CH=CHC(6)H(4)Me-4, C(C≡CPh)=CHPh). Two osmium analogues, Os(CH=CHC(6)H(4)Me-4)(κ(2)-S(2)C·IMes)(CO)(PPh(3))(2) and Os(C(C≡CPh)=CHPh)(κ(2)-S(2)C·IMes)(CO)(PPh(3))(2) were also prepared. When the more bulky diisopropylphenyl derivative IDip·CS(2) is used, an unusual product, Ru(κ(2)-SC(H)S(CH=CHC(6)H(4)Me-4)·IDip)Cl(CO)(PPh(3))(2), with a migrated vinyl group, is obtained. Over extended reaction times, [Ru(CH=CHC(6)H(4)Me-4)Cl(BTD)(CO)(PPh(3))(2)] also reacts with IMes·CS(2) and NH(4)PF(6) to yield the analogous product Ru{κ(2)-SC(H)S(CH=CHC(6)H(4)Me-4)·IMes}Cl(CO)(PPh(3))(2)via the intermediate Ru(CH=CHC(6)H(4)Me-4)(κ(2)-S(2)C·IMes)(CO)(PPh(3))(2). Structural studies are reported for [Ru(CH=CHC(6)H(4)Me-4)(κ(2)-S(2)C·IPr)(CO)(PPh(3))(2)]PF(6) and [Ru(C(C≡CPh)=CHPh)(κ(2)-S(2)C·ICy)(CO)(PPh(3))(2)]PF(6).