FACILE DEPROTONATION OF THE HYDROGENSULFIDO LIGAND IN [MN2(MU-H)(MU-SH)(CO)6(DIPHOSPHINE)] COMPLEXES

The unsaturated dihydrides [Mn2(mu-H)2(CO)6(mu-L-L)] [L-L = Ph2PCH2PPh2 (dppm) 1; or (EtO)2-POP(OEt)2 (tedip) 2] react with sulfur to yield the hydrogensulfido complexes [Mn2(mu-H)(mu-SH)(CO)6(mu-L-L-] (L-L = dppm 3a; or tedip 3b). The hydrogen bound to the sulfur atom in 3a is easily removed by thallium(1) acetylacetonate, generating a species which affords, upon reaction with the appropriate electrophiles, the thiolato complexes [Mn2(mu-H)(mu-SZ)(CO)6(mu-dppm)] (Z = Me 3c, SnMe3 3d, or AuPPh3 3e). The solid-state structure of 3e has been determined by X-ray methods [monoclinic, space group P2(1)/n, a = 1 8.840 (4), b = 1 3.024 (2), c = 20.243 (4) angstrom, beta = 108.66 (2)-degrees, Z = 4].