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An Electron-Deficient Triosmium Cluster Containing the Thianthrene Ligand: Synthesis, Structure and Reactivity of [Os3(CO)9(μ3-η2-C12H7S2)(μ-H)]

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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)9(μ3-η2-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.

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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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Authors and Affiliations

  1. Department of Chemistry, Jahangirnagar University, Savar, Dhaka, 1342, Bangladesh

    Arun K. Raha, Mohammad R. Hassan, Shariff E. Kabir & Md. Manzurul Karim

  2. Department of Chemistry, University of Waikato, Hamilton, New Zealand

    Brian K. Nicholson

  3. Department of Chemistry, The University of Montana, Missoula, Montana, 59812, USA

    Ayesha Sharmin, Luca Salassa & Edward Rosenberg

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  1. Arun K. Raha
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Correspondence to Edward Rosenberg.

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Dedicated to the memory of a great scientist, F. Albert Cotton.

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Raha, A.K., Hassan, M.R., Kabir, S.E. et al. An Electron-Deficient Triosmium Cluster Containing the Thianthrene Ligand: Synthesis, Structure and Reactivity of [Os3(CO)9(μ3-η2-C12H7S2)(μ-H)]. J Clust Sci 19, 47–62 (2008). https://doi.org/10.1007/s10876-007-0158-1

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