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Updated: Jun 11, 2026

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
Osmium-bismuth complexes from the reaction of Os3(CO)11(NCMe) with BiPh3
Richard D Adams1, William C Pearl
1Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, USA. adams@mail.chem.sc.edu
Abstract:
Five new compounds were obtained from the reaction of Os(3)(CO)(11)(NCMe), 1, with BiPh(3) in hexane solution at reflux. These have been identified as Os(2)(CO)(8)(mu-BiPh), 2, Os(CO)(4)Ph(2), 3, Os(4)(CO)(14)(mu-eta(3)-O=CC(6)H(5))(mu(4)-Bi), 4, Os(4)(CO)(15)Ph(mu(4)-Bi), 5, and Os(5)(CO)(19)Ph(mu(4)-Bi), 6. Cleavage of the phenyl groups from the BiPh(3) was the dominant reaction pathway. Fragmentation of the original triosmium cluster was accompanied by reaggregation processes that were facilitated by the naked bismuth to yield the higher nuclearity osmium cluster complexes containing spiro-bridging bismuth ligands. Compound 6 was photo-decarbonylated to yield the compound HOs(5)(CO)(18)(mu-eta(2)-C(6)H(4))(mu(4)-Bi), 7, formed by ortho-CH activation of the sigma-bonded phenyl ring in 6 to form a bridging eta(2)-benzyne ligand. Compounds 2- 7 were each characterized structurally by a single-crystal X-ray diffraction analysis.
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