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(μ-H)(μ-X){SMe(But)}] (X = H, OH)

Reaction of [Os-3(CO)(11)(NCMe)] with R2S (R = Et, Pr-n) and MeSBu' results in the formation of [Os-3(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 [Os-3(CO)(10)(NCMe)(2)] is reacted with R2S (R = Et, Pr-n) while reaction of the same cluster with Ph,S or MeSPh results in the formation of orthometallated clusters, viz. [Os-3(mu -H)(CO)(10)(mu-eta (2)-C6H4SR)] and [Os-3(mu -H)(CO)(9)(mu (3)- C6H4SPh)]. The similar reaction of [Os-3(mu -H)(2)(CO)(10)] with Pr2S, MeSBu'. 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 [Os-3(CO)(9)(mu -H)(2)(thioether)]. The crystal and molecular structures of [Os-3(CO)(11)(L)] (L=Et2S, Pr2S, S(CH2)(5)) and [Os-3(CO)(9)(mu -H)(mu -X){SMe(Bu')}] (X = H, OH) are presented. (C)' 2001 Elsevier Science B.V. All rights reserved.