Bis(mercapto) and hydrido(thiolate) complexes of Ru(II)–dppm (dppm=Ph2PCH2PPh2)

From a mixture of cis- and trans-Ru(SH)2(dppm)2 (4), formed from reaction of H2S with trans-Ru(H)Cl(dppm)2 (2), a crystal of cis-4 has been isolated and its structure determined by X-ray analysis. The mercapto protons are located within the centrosymmetric structure, although the S-atoms are partially disordered (S–H∼1.06 Å). The thiolate complexes, trans-Ru(H)SR(dppm)2 (R=Ph, 5a; C6F5, 5b), have been isolated from reaction of trans-2 with 1 equiv. of RSH. trans-Ru(H)SH(dppm)2 (3) has been isolated from reaction of H2S with a mixture of cis- and trans-Ru(H)2(dppm)2 (1). An improved synthetic route for 1 is presented.