Cluster build-up reactions via the ionic coupling of tetraosmium anions and the [RhCp*(NCMe)3]2+ cation; The crystal and molecular structures of [Os4Rh(μ-H)3(MeC=NH)(CO)115-Cp*)], [Os4Rh(μ-H)2(CO)135-Cp *)]

William Clegg, Neil Feeder, Ana M. Martin Castro, Saifun Nahar, Paul R. Raithby, Gregory P. Shields, Simon J. Teat

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Abstract

The reaction of [Os4H4(CO)11]2- 2, formed by the reduction of [Os4H4(CO)12] 1 with K/Ph2CO, with the cation [Rh(η5-Cp*)(MeCN)3]2+ (Cp*=C5Me5) 3, affords a number of penta- and hexanuclear mixed-metal clusters depending on the reaction conditions. If only sufficient K/Ph2CO is added to dissolve all of 1, and the dication 3 added, a low yield of a blue cluster [Os4Rh(μ-H)3(MeC=NH)(CO)115-Cp*)] (Cp*=C5Me5) 4 is obtained in addition to large quantities of 1. If an excess of K/Ph2CO is added so that reduction of 1 is complete, and then the dication 3 added, two new products [Os4Rh(μ-H)2(CO)135-Cp*)] 5 and [Os4Rh2(μ-H)2(CO)115-Cp*)2] 6 are obtained in low yield. The three new complexes have been characterised spectroscopically and crystallographically. Cluster 4 contains the uncommon MeC=NH group coordinated to an edge-bridged tetrahedral metal framework. The metal framework in 5 is also a Rh edge-bridged Os4 tetrahedron while that of 6 is a bicapped tetrahedron, with two Rh atoms face capping two faces of an Os4 tetrahedron.

Original languageEnglish
Pages (from-to)237-246
Number of pages10
JournalJournal of Organometallic Chemistry
Volume573
Issue number1-2
DOIs
Publication statusPublished - 31 Jan 1999

Funding

We thank the EPSRC for financial support for the purchase of instrumentation and for fellowships (to N.F. and S.J.T) and for a studentship (to G.P.S). We gratefully acknowledge the financial support of the Cambridge Commonwealth Trust and the United Kingdom Committee of Vice Chancellors and Principals (to S.N.), the Cambridge crystallographic data centre (to G.P.S.), and the CCLRC (to W.C.). A.M.M.C. wishes to thank the Spanish Ministry of Education and the British Council for a grant and for study leave. We are grateful to Johnson Matthey for a generous loan of osmium and rhodium salts.

Keywords

  • Cluster
  • Crystal structures
  • Cyclopentadienyl
  • Osmium
  • Rhodium

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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