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The role of the phosphorus lone pair in the low-energy binuclear phospholyl vanadium carbonyl structures: comparison with cyclopentadienyl analogues

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Abstract

The structures and energetics of the binuclear phospholyl vanadium carbonyls (C4H4P)2V2(CO)n (n = 7, 6, 5, 4, 3, 2, 1) have been investigated using density functional theory. The lowest energy heptacarbonyl (C4H4P)2V2(CO)7 structures resemble those of the dimanganese pentacarbonyl (C4H4P)2Mn2(CO)5 with one seven-electron donor bridging η5,η1-C4H4P ring and no direct vanadium–vanadium bond. Similarly, the lowest energy hexacarbonyl (C4H4P)2V2(CO)6 structure resembles that of the dimanganese tetracarbonyl (C4H4P)2Mn2(CO)4 with two seven-electron donor bridging η5,η1-C4H4P rings and no direct vanadium–vanadium bond. The lowest energy pentacarbonyl (C4H4P)2V2(CO)5 structure has terminal η5-C4H4P phospholyl rings and a formal V≡V triple bond of length ~ 2.45 Å similar to the experimentally known and structurally characterized cyclopentadienyl analogue (η5-C5H5)2V2(CO)5. Various combinations of V=V double bonds or V≡V triple bonds, four-electron donor bridging carbonyl groups and seven-electron donor bridging η5,η1-C4H4P rings are found in the more highly unsaturated derivatives (C4H4P)2V2(CO)n (n = 4, 3, 2) to give 17- and 18-electron vanadium configurations for triplet- and singlet-state structures, respectively. Formal V≣V quadruple bonds are found only in the highly unsaturated lowest energy singlet (C4H4P)2V2(CO)n (n = 2, 1) structures, which, however, lie at somewhat higher energies than isomeric triplet structures.

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Acknowledgements

We are indebted to the Scientific Research Fund of the Key Laboratory of the Education Department of Sichuan Province (Grant No. 10ZX012) for the support of this research.

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Authors and Affiliations

  1. School of Sciences, Research Center for Advanced Computation, Xihua University, Chengdu, China, 610039

    Wenqian Chen, Jun Yan, Xiaohong Chen, Rong Jin & Quan Du

  2. Department of Chemistry, Center for Computational Quantum Chemistry, University of Georgia, Athens, GA, 30602, USA

    Yaoming Xie & R. Bruce King

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  1. Wenqian Chen
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  2. Jun Yan
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  3. Xiaohong Chen
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Correspondence to Xiaohong Chen or R. Bruce King.

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Chen, W., Yan, J., Chen, X. et al. The role of the phosphorus lone pair in the low-energy binuclear phospholyl vanadium carbonyl structures: comparison with cyclopentadienyl analogues. Theor Chem Acc 140, 3 (2021). https://doi.org/10.1007/s00214-020-02692-y

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