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Carbon-hydrogen bond activation in bridging cyclobutadiene ligands in unsaturated binuclear vanadium carbonyl derivatives

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Abstract

The structures and energetics of the binuclear cyclobutadiene vanadium carbonyls (C4H4)2V2(CO)n (n = 8, 7, 6, 5, 4, 3, 2) have been investigated by density functional theory (DFT). The lowest energy (C4H4)2V2(CO)8 structure consists of two C4H4V(CO)4 units linked by a V-V single bond of length 3.4 Å. The two lowest energy (C4H4)2V2(CO)7 structures also have formal V-V single bonds. The “extra” two electrons to give each vanadium atom in these heptacarbonyls the favored 18-electron configuration can come from either an agostic C-H-V interaction activating a hydrogen atom from one of the cyclobutadiene rings or from a four-electron donor bridging η2-µ-CO group with a short V–O distance. The lowest energy (C4H4)2V2(CO)6 structure has a formal V≡V triple bond of length 2.52 Å similar to the V≡V triple bond of length 2.46 Å found in the experimentally known cyclopentadienyl derivative (η5-C5H5)2V2(CO)5. The lowest energy structures for the more highly unsaturated (C4H4)2V2(CO)n (n = 5, 4, 3, 2) have at least two four-electron donor bridging η2-µ-CO groups and a vanadium-vanadium bond order sufficient to give each vanadium atom at least a 16-electron configuration.

Graphical abstract

The structures and energetics of the binuclear cyclobutadiene vanadium carbonyls (C4H4)2V2(CO)n (n = 8, 7, 6, 5, 4, 3, 2) have been investigated by density functional theory. The two lowest energy (C4H4)2V2(CO)7 structures include one with an agostic C-H-V interaction activating a hydrogen atom from one of the cyclobutadiene rings and another with a four-electron donor bridging η2-µ-CO group with a short V–O bonding distance.

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Data availability

The atomic coordinates, total energies, HOMO–LUMO gaps, and the harmonic vibrational frequencies for all optimized structures are available in the Supporting Information.

Code availability

Commercially available Gaussian programs were used for the calculations as indicated; no custom codes were developed or used.

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Funding

We are indebted to the New Century Excellent Talents in University (Grant No, NCET-10–0949), the Scientific Research Fund of the Key Laboratory of the Education Department of Sichuan Province in China (Grant No. 10ZX012), and the Innovation Fund of Postgraduate, Xihua University (Grant No. ycjj2019099 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, 610039, China

    Chongyao Song, Qifa Liu, Wenqian Chen, Xiaohong Chen, Rong Jin & Quan Du

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

    Yaoming Xie & R. Bruce King

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  1. Chongyao Song
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  2. Qifa Liu
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  7. Yaoming Xie
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Correspondence to Xiaohong Chen or R. Bruce King.

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Song, C., Liu, Q., Chen, W. et al. Carbon-hydrogen bond activation in bridging cyclobutadiene ligands in unsaturated binuclear vanadium carbonyl derivatives. J Mol Model 28, 39 (2022). https://doi.org/10.1007/s00894-021-05009-3

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