Facile deprotonation of the hydrogensulfido ligand in [Mn2(µ-H)(µ-SH)(CO)6(diphosphine)] complexes

Abstract

The unsaturated dihydrides [Mn₂(µ-H)₂(CO)₆(µ-L–L)][L–L = Ph₂PCH₂PPh₂(dppm)1; or (EtO)₂POP(OEt)₂(tedip)2] react with sulfur to yield the hydrogensulfido complexes [Mn₂(µ-H)(µ-SH)(CO)₆(µ-L–L)](L–L = dppm 3a; or tedip 3b). The hydrogen bound to the sulfur atom in 3a is easily removed by thallium(I) acetylacetonate, generating a species which affords, upon reaction with the appropriate electrophiles, the thiolato complexes [Mn₂(µ-H)(µ-SZ)(CO)₆(µ-dppm)](Z = Me 3c, SnMe₃3d, or AuPPh₃3e). The solid-state structure of 3e has been determined by X-ray methods [monoclinic, space group P2₁/n, a= 18.840(4), b= 13.024(2), c= 20.243(4)Å, β= 108.66(2)°, Z= 4].