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An overview of the electronic structure in trigonal bipyramidal clusters of main elements or mixed with transition metals

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Abstract

Equatorial/apical bond repartitioning in TBP clusters, formed by main group elements only (e.g., B5H5 2−, B3H3N2, etc.) or mixed with metal atoms (e.g., [(L2M)3S2]n, [(L3M)3S2]n, [(CpM)3S2]n), is critically analyzed from the horizontal comparison of the experimental structures and in terms of basic MO concepts. The ideas are double-checked through specific DFT calculations or existing ab initio results. Based on the Wade’s rules for closo-clusters, the five vertices systems are normally characterized by six skeletal electron pairs. In the main group clusters, the electron delocalization at the equatorial edges depends on the electronegativity of the apical groups and for the Beq–Beq bonds an inverse relationship between bond strength and bond length is remarked. In [(L2M)3S2]n compounds with a total electron count (TEC) of 48, the six bonding electron pairs localize at the apical M–S bonds. In [(L3M)3S2]n or [(CpM)3S2]n, also with TEC = 48, the effective atomic number rule predicts three single M–M single bonds besides the six M–S apical ones. In actuality, only partial M–M bonding can be considered due to the intermediation of the capping sulphur atoms, that help shifting the antibonding character of populated radial levels with that of the vacant tangential ones (bonding). The qualitative MO arguments are supported by the topological nature of the calculated DFT wave functions. Moreover, the MO nature of three lowest LUMOs for 48e− species help to rationalize experimental structural trends observed for the addition of up to five electrons.

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Notes

  1. Cambridge Structural Database System, Cambridge Crystallographic data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK.

  2. The EAN rule predicts that the number of M–M bonds (n) is equal to the half difference between the highest electron configuration achievable by all the metals (in this case 3 × 18) and the actual number of valence electrons (=TEC). For 48e− TBP compounds, n = 3.

  3. To justify some experimental data it has been assumed that a2′ may even be lower than 2e′ [55].

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Acknowledgments

Thanks are expressed to Professor Roald Hoffmann for comments and suggestions. The work was carried out under the Project No. 7 of the DPM at CNR. Computations have performed thanks to the time allotted by CINECA and CASPUR under the agreement with CNR.

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  1. Istituto di Chimica dei Composti Organometallici, ICCOM-CNR, Via Madonna del Piano 10, 50019, Sesto Fiorentino (Florence), Italy

    Carlo Mealli, Abdelatif Messaoudi & Andrea Ienco

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  1. Carlo Mealli
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  2. Abdelatif Messaoudi
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Correspondence to Carlo Mealli.

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Dedicated to the memory of Professor Oriano Salvetti and published as part of the Salvetti Memorial Issue.

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Mealli, C., Messaoudi, A. & Ienco, A. An overview of the electronic structure in trigonal bipyramidal clusters of main elements or mixed with transition metals. Theor Chem Acc 123, 365–373 (2009). https://doi.org/10.1007/s00214-009-0563-7

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