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Journal of Cluster Science

, Volume 19, Issue 1, pp 47–62 | Cite as

An Electron-Deficient Triosmium Cluster Containing the Thianthrene Ligand: Synthesis, Structure and Reactivity of [Os3(CO)932-C12H7S2)(μ-H)]

  • Arun K. Raha
  • Mohammad R. Hassan
  • Shariff E. Kabir
  • Md. Manzurul Karim
  • Brian K. Nicholson
  • Ayesha Sharmin
  • Luca Salassa
  • Edward Rosenberg
Original Paper

Abstract

Reaction of [Os3(CO)10(CH3CN)2] with thianthrene at 80 °C leads to the nonacarbonyl dihydride compound [Os3(CO)9(μ-3,4-η2-C12H6S2)(μ-H)2] (1) and the 46-electron monohydride compound [Os3(CO)932-C12H7S2)(μ-H)] (2). Compound 2 reacts reversibly with CO to give the CO adduct [Os3(CO)10(μ-η2-C12H7S2)(μ-H)] (3) whereas with PPh3 it gives the addition product [Os3(CO)9)(PPh3)(μ-η2-C12H7S2)(μ-H)] (4) as well as the substitution product 1,2-[Os3(CO)10((PPh3)2] (5) Compound 2 represents a unique example of an electron-deficient triosmium cluster in which the thianthrene ring is bound to cluster by coordination of the sulfur lone pair and a three-center-two-electron bond with the C(2) carbon which bridges the same edge of the triangle as the hydride. Electrochemical and DFT studies which elucidate the electronic properties of 2 are reported.

Keywords

Triosmium cluster Thianthrene Electron-deficient Ligand addition DFT 

Notes

Acknowledgments

We thank Dr. Tania Groutso, University of Auckland for collection of X-ray intensity data. One of us (AKS) gratefully acknowledges the University Grants Commission of Bangladesh for a Scholarship. Support for this research by the Department of Energy (E.R., grant # DE-FG02-01ER45869) is also gratefully acknowledged.

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Copyright information

© Springer Science+Business Media, LLC 2007

Authors and Affiliations

  • Arun K. Raha
    • 1
  • Mohammad R. Hassan
    • 1
  • Shariff E. Kabir
    • 1
  • Md. Manzurul Karim
    • 1
  • Brian K. Nicholson
    • 2
  • Ayesha Sharmin
    • 3
  • Luca Salassa
    • 3
  • Edward Rosenberg
    • 3
  1. 1.Department of ChemistryJahangirnagar UniversityDhakaBangladesh
  2. 2.Department of ChemistryUniversity of WaikatoHamiltonNew Zealand
  3. 3.Department of ChemistryThe University of MontanaMissoulaUSA

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