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Rational Synthesis of Molybdenum(V) Tetramers Consisting of [Mo2O4]2+ Dimers Held Together by Bridging Phosphinate Ligands and the Tungsten(VI) Dimer [(CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2]: Structural and Theoretical Considerations

Journal of Cluster Science volume 19, pages 181–195 (2008)Cite this article

Abstract

Reacting MoO2(acac)2 with Ph2POOH or Me2POOH in EtOH results in the formation of the tetranuclear molybdenum (V) clusters Mo4(μ 3-O)4(μ-O2PR2)4O4, PR2 = PPh2, 1, or PMe2, 2, in functional yields (>90% and 55% respectively). The reaction of WO2(acac)2 with Ph2POOH in MeOH affords the tungsten dimer [(CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2], 3. The single crystal X-ray determined structures of complexes 1–3 are reported. In 1 and 2, the four Mo=O units are interconnected by four triply bridging oxygen atoms, resulting in a distorted cubic-like structure for the Mo4(μ 3-O)4O4 units. Each molybdenum atom forms two additional Mo–O bonds with two oxygen atoms from different adjacent phosphinato ligands. Complex 3, a tungsten dimer, contains packing disorder and consists of bridging oxo and diphenylphosphinato ligands. The bonding of 1 and 2 assessed by density-functional methods showed that bonding between the Mo(V) centers occurs through σ overlap of the d xy orbitals.

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Acknowledgment

We thank Michigan Technological University for support of this research.

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Authors and Affiliations

  1. Department of Chemistry, Michigan Technological University, 1400 Townsend Drive, Houghton, MI, 49931, USA

    Ampa Jimtaisong, Linsheng Feng, Soumya Sreehari & Rudy L. Luck

  2. Department of Chemistry and Biochemistry, Old Dominion University, Hampton Boulevard, Norfolk, VA, 23529, USA

    Craig A. Bayse

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  1. Ampa Jimtaisong
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  2. Linsheng Feng
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  4. Craig A. Bayse
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Correspondence to Rudy L. Luck.

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Dedicated to the memory of Professor F. A. Cotton. Veritas numquam perit.

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Jimtaisong, A., Feng, L., Sreehari, S. et al. Rational Synthesis of Molybdenum(V) Tetramers Consisting of [Mo2O4]2+ Dimers Held Together by Bridging Phosphinate Ligands and the Tungsten(VI) Dimer [(CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2]: Structural and Theoretical Considerations. J Clust Sci 19, 181–195 (2008). https://doi.org/10.1007/s10876-007-0170-5

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  • DOI: https://doi.org/10.1007/s10876-007-0170-5

Keywords

  • Oxo molybdenum
  • Tetranuclear cluster
  • Distorted cube
  • Diphenylphosphinic acid
  • Oxo-bridged tungsten dimer

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