Journal
JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume 623, Issue 1-2, Pages 191-201Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/S0022-328X(01)00643-X
Keywords
osmium; cluster; thioether; hydrodesulfurization; crystal structure
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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.
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