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Synthesis and structural characterization of a diruthenium pentalene complex, \([\hbox {Cp}^{*}\hbox {Ru}\{(\hbox {Cp}^{*}\hbox {Ru})_{2}\hbox {B}_{6}\hbox {H}_{14}\}(\hbox {Cp}^{*}\hbox {Ru})]\)

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Abstract

Abstract 

Treatment of nido-[1,2-(Cp*Ru)\(_{2}\)(\(\mu \)-H)\(_{2}\)B\(_{3}\)H\(_{7}\)], 1 with five equivalents of Te powder led to the isolation of diruthenium pentalene analogue \([(\hbox {Cp*}\hbox {Ru})\{(\hbox {Cp*}\hbox {Ru})_{2}\hbox {B}_{6}\hbox {H}_{14}\}(\hbox {RuCp*})]\), 2 and a metal indenyl complex \([(\hbox {Cp*}\hbox {Ru})_{2}\hbox {B}_{2}\hbox {H}_{6}\hbox {C}_{6}\hbox {H}_{3}(\hbox {CH}_{3})\)], 3. The \([(\hbox {Cp*}\hbox {Ru})_{2}\hbox {B}_{6}\hbox {H}_{14}\)] fragment in 2 may be considered as a true metal–boron analogue of \(\upeta ^{5}\)-\(\upeta ^{5}\)-pentalene ligand (\(\hbox {C}_{8}\hbox {H}_{6})\) and \([(\hbox {Cp*}\hbox {Ru})\hbox {B}_{2}\hbox {H}_{6}\hbox {C}_{6}\hbox {H}_{3}(\hbox {CH}_{3})\)] fragment in 3 is an analogue of \(\upeta ^{5}\)-indenyl ligand. The solid-state X-ray structures were unambiguously determined by crystallographic analysis of compounds 2 and 3. Further, the density functional theory (DFT) calculations were performed to investigate the bonding and the electronic properties of 2a (Cp analogue of 2). The frontier molecular orbital analysis of both 2a and 2b (Cp analogue of \([(\hbox {Cp*}\hbox {Ru})\hbox {B}_{8}\hbox {H}_{14}(\hbox {RuCp*})])\) reveals a lower HOMO–LUMO gap indicating less thermodynamic stability.

Graphical Abstract

SYNOPSIS Treatment of nido-[1,2-(Cp\({*}\)Ru)\(_{2}(\upmu \)-H)\(_{2}\)B\(_{3}\)H\(_{7}\)] with Te powder led to the isolation of diruthenium pentalene analogue \([(\hbox {Cp*}\hbox {Ru})\{(\hbox {Cp*}\hbox {Ru})_{2}\hbox {B}_{6}\hbox {H}_{14}\}(\hbox {RuCp*})]\) and a metal indenyl complex \([(\hbox {Cp*}\hbox {Ru})_{2}\hbox {B}_{2}\hbox {H}_{6}\hbox {C}_{6}\hbox {H}_{3}(\hbox {CH}_{3})\)].

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Acknowledgements

The generous support of the Council of Scientific & Industrial Research, CSIR (Project No. 01(2837)/15/EMR-II), New Delhi, India, is gratefully acknowledged. B.J. and S.K.B. thank UGC and IIT Madras for research fellowships. We are very thankful to Dr. Bijan Mondal for scientific discussion. We thank Dr. Babu Varghese (SAIF, IIT Madras) for X-ray data analysis. IIT Madras is gratefully acknowledged for computational facilities.

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

    Benson Joseph, Subrat Kumar Barik, Soumya Kumar Sinha & Sundargopal Ghosh

  2. Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1, 35042, Rennes Cedex, France

    Thierry Roisnel

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  1. Benson Joseph
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Joseph, B., Barik, S.K., Sinha, S.K. et al. Synthesis and structural characterization of a diruthenium pentalene complex, \([\hbox {Cp}^{*}\hbox {Ru}\{(\hbox {Cp}^{*}\hbox {Ru})_{2}\hbox {B}_{6}\hbox {H}_{14}\}(\hbox {Cp}^{*}\hbox {Ru})]\). J Chem Sci 130, 89 (2018). https://doi.org/10.1007/s12039-018-1479-3

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