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Theoretical Study of the Distortion from Regular Tetrahedral Structure of M(NH2)4 Complexes

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Abstract

Theoretical study on tetrakis-amido complexes (M(NR2)4, M = Ti, V, Cr, and Mo; R = H, Me) is presented. At first a rough investigation of the potential energy surface indicates that all stationary points are of S 4 or D 2 symmetry depending on the coupled rotations of the NR2 groups. Qualitative correlation diagrams are calculated within S 4 or D 2 symmetry constraint between two limiting structures of D 2 d symmetry. DFT (B3LYP) calculations on these two paths are presented for unsubstituted complexes (R = H) and the various minima are optimized and characterized. These results are discussed in the light of the correlation diagrams. Finally, optimization of the different minima has been performed on substituted species (R = Me) and the theoretical results are shown to be in good agreement with the experimental structural determination when available.

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  1. Paul Fleurat-Lessard

    Present address: Laboratoire de Chimie, Ecole Normale Supérieure de Lyon, 46, Allée d’Italie, 69364, Lyon Cedex 07, France

  2. François Volatron

    Present address: Laboratoire de Chimie Théorique, Faculté des Sciences de Jussieu Université Paris VI, 3 rue Galilée, 94200, IVRY, France

Authors and Affiliations

  1. Laboratoire de Chimie Physique (CNRS-UMR8000), Université de Paris-Sud, Bât. 490, 91405, Orsay Cedex, France

    Paul Fleurat-Lessard & François Volatron

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  1. Paul Fleurat-Lessard
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  2. François Volatron
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Correspondence to François Volatron.

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Fleurat-Lessard, P., Volatron, F. Theoretical Study of the Distortion from Regular Tetrahedral Structure of M(NH2)4 Complexes. Theor Chem Acc 116, 718–725 (2006). https://doi.org/10.1007/s00214-006-0118-0

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  • DOI: https://doi.org/10.1007/s00214-006-0118-0

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