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Syntheses and structures of chalcogen-bridged binuclear group 5 and 6 metal complexes

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Abstract

Syntheses and structural elucidations of a series of chalcogen stabilized binuclear complexes of group 5 and 6 transition metals have been described. Room temperature reaction of [Cp*CrCl]2 (Cp* = η5-C5Me5) with Li[BH3(SePh)] afforded a Se inserted binuclear chromium complex, [(Cp*Cr)2(µ-Se2SePh)2], 1. In an attempt to make the analogous complexes with heavier group 6 metals, reactions of [Cp*MCl4] (M = Mo and W) with Li[BH3(SePh)] were carried out that yielded Se inserted binuclear complexes [(Cp*M)2(µ-Se)2(µ-SePh)2], 2 and 3 (2: M = Mo and 3: M = W) along with known [(Cp*M)2B5H9], 4a–b (4a: M = Mo and 4b: M = W). Similarly, the reactions of [Cp*NbCl4] with Li[BH3(EPh)] (E = S or Se) followed by thermolysis led to the formation of binuclear chalcogen complexes [(Cp*Nb)2(µ-E2)2], 5 and 6 (5: E = S and 6: E = Se) and known [(Cp*Nb)2(B2H6)2], 7. All these complexes have been characterized by 1H and 13C NMR spectroscopy and mass spectrometry. The structural integrity of complexes 1, 3, 5 and 6 was established by the X-ray diffraction studies. The DFT studies further exemplify the bonding interactions present in these complexes, especially the multiple bond character between the metals in 1–3.

Graphic abstract

The syntheses and structural characterizations of three chalcogen-bridged bimetallic complexes of group 5 and 6 metals, such as [(Cp*Nb)2(µ-E2)2] (E = S and Se) (right), [(Cp*Cr)2(µ-Se2SePh)2] (centre) and [(Cp*M)2(µ-Se)2(µ-SePh)2], (M = Mo and W) (left) are reported.

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  • 22 January 2020

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Acknowledgements

This work was supported by the Council of Scientific & Industrial Research (CSIR) (Project No. 01(2939)/18/emr-ii), New Delhi, India. DST-FIST, India, is gratefully acknowledged for the HRMS facility. M. B., R. P., M. G. C. and B. R. are grateful to IIT Madras and C.N. is grateful to DST-INSPIRE, India for fellowship. The computational facility of IIT Madras is gratefully acknowledged. We thank Dr. C. Ghosh for X-ray data collection and Dr. B. Varghese and Mr. V. Ramkumar for X–ray structure analysis.

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  1. Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600 036, Tamilnadu, India

    Moulika Bhattacharyya, Rini Prakash, Chandan Nandi, Monojit Ghosal Chowdhury, Beesam Raghavendra & Sundargopal Ghosh

  2. CNRS, ISCR (Institut des Sciences Chimiques de Rennes) – UMR 6226, Univ Rennes, 35000, Rennes, France

    Thierry Roisnel

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  1. Moulika Bhattacharyya
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Bhattacharyya, M., Prakash, R., Nandi, C. et al. Syntheses and structures of chalcogen-bridged binuclear group 5 and 6 metal complexes. J Chem Sci 131, 123 (2019). https://doi.org/10.1007/s12039-019-1703-9

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