Synthesis and characterization of new thioether derivatives of [Os3(CO)12] and [H2Os3(CO)10]; crystal and molecular structures of [Os3(CO)11(L)] [Et2S, Pr2S, S(CH2)5] and [Os3(CO)9(m-H)(m-X){SMe(But)}] (X = H, OH)

Reaction of [Os3(CO)11(NCMe)] with R2S (R = Et, nPr) and MeSBut results in the formation of [Os3(CO)11(L)] (L = thioether) clusters in which the thioethers are coordinated in an equatorial site of the triosmium framework. Such monosubstituted clusters are also formed when [Os3(CO)10(NCMe)2] is reacted with R2S (R = Et, nPr) while reaction of the same cluster with Ph2S or MeSPh results in the formation of orthometalated clusters, viz. [Os3(m-H)(CO)10(m-h2-C6H4SR)] and [Os3(m-H)(CO)9(m3-C6H4SPh)]. The similar reaction of [Os3(m-H)2(CO)10] with Pr2S, MeSBut, MeSPh or Ph2S does not lead to discernable products except when carried out in the presence of trimethylamine N-oxide, which leads to clusters of the general formula [Os3(CO)9(m-H)2(thioether)]. The crystal and mol. structures of [Os3(CO)11(L)] (L = Et2S, Pr2S, S(CH2)5) and [Os3(CO)9(m-H)(m-X){SMe(But)}] (X = H, OH) are presented.