NEW UNSATURATED-DITHIOLATE-BRIDGED RHODIUM COMPLEXES

The preparation of the homobinuclear complexes [Rh-2 (mu-SS)COD)(2)]SS =1,1-dicyanoethene-1,2-dithiolate (1,1-MNT) 1 or 1,2-dicyanoethene-1,2 -dithiolate (1,2-MNT) 2, [Rh-2(mu-S S) (CO)(4)] SS=1,1-MNT 3, 1,2-MNT 4 are reported. Compounds 3 and 4 react with stoichiometric quantities of PPh(3) and dppm (bis(diphenylphosphino) methane) leading to [Rh-2 mu-SS) (CO)(2)(PPh(3))(2)]=SS-1,1-MNT 5, 1,2-MNT 6, [Rh-2(mu-SS)(mu-dp pm)(2)(CO)(2)] SS=1,1-MNT 7,1,2-MNT 8, and [Rh-2(mu-S)(mu-dppm)(2)(CO) (2)]SS= 1,1-MNT 9, 1,2-MNT 10. Reaction of [NBu(4)][Rh(SS)(COD)] and [ Ir(COD)(acetone)(2)] [BF4] lead to the heterobimetallic complexes [(CO D)Rh(mu-SS)Ir(COD)]SS=1,1-MNT 11, 1,2-MNT 12. Addition of mercury(II)c hloride to complex 6 gave the binuclear rhodium(II) compound [Rh-2(mu- 1,2-MNT) Cl-2(CO)(2)(PPh(3))(2)] 13. Complex 6 undergoes addition of m olecular iodine yielding [Rh-2(mu-1,2-MNT)I-2(CO)(2)(PPh(3))(2)] 14.