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Electronic, geometrical, and thermochemical studies on group-14 element-diruthenaborane cluster compounds: a theoretical investigation

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Abstract

Density functional theory (DFT) calculations were used to probe the reaction of the diruthenaborane nido-[1,2-(Cp*RuH)2B3H7] (Cp* = η5-C5Me5), (1) with MeC ≡ CMe to form the major product nido-[1,2-(Cp*Ru)2(μ-H)(μ-BH2)-4,5-Me2-4,5-C2B2H4] (2) along with minor product nido-(Cp*Ru)2-4,5-Me2-4,5-C2B2H6 (3). The structural features of the other related diruthenacarboranes, nido-(Cp*Ru)2-4,5-Me2-4,5-C2B2H6 (4) and closo-1,2-(Cp*RuH)2-4,5-Me2-4,5-C2B3H3 (5), were also studied. Since metallaheteroboranes with p-block group-14 elements are rare, we extend our DFT studies to explore the reaction of 1 with heavier group-14 alkyne analogs, RE ≡ ER (E = Si, Ge, and Sn; R = alkyl or aryl groups). The geometrical and electronic structures of the products nido-[1,2-(Cp*Ru)2(μ-H)(μ-BH2)-4,5-Me2-4,5-E2B2H4] (E = Si (6), Ge (7), Sn (8)) are described and compared with the ruthenacarborane analog, nido-[1,2-(Cp*Ru)2(μ-H)(μ-BH2)-4,5-Me2-4,5-C2B2H4] species, 2. The computed energetics and the geometries support the feasibility of the reaction and the stability of the products. NBO analysis was performed to delve further into the nature of the bonding in this kind of clusters.

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Acknowledgments

The authors acknowledge the Indo-French Centre for Promotion of Advanced Research (IFCPAR) (Project No. 4405-1) for financial support.

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Authors and Affiliations

  1. Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, 35042, Rennes Cedex, France

    Bellie Sundaram Krishnamoorthy, Samia Kahlal & Jean-François Halet

  2. Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600036, India

    Sundargopal Ghosh

Authors
  1. Bellie Sundaram Krishnamoorthy
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  2. Samia Kahlal
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  3. Sundargopal Ghosh
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  4. Jean-François Halet
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Corresponding authors

Correspondence to Bellie Sundaram Krishnamoorthy or Jean-François Halet.

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Supplementary material 1 Cartesian coordinates of all calculated geometries. (DOC 62 kb)

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Krishnamoorthy, B.S., Kahlal, S., Ghosh, S. et al. Electronic, geometrical, and thermochemical studies on group-14 element-diruthenaborane cluster compounds: a theoretical investigation. Theor Chem Acc 132, 1356 (2013). https://doi.org/10.1007/s00214-013-1356-6

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