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Theoretical study of the bent U(η8-C8H8)2(CN)− complex

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Abstract

The ground-state electronic structure of the cyanido complex [U(η8-C8H8)2(CN)]− as well as the thermodynamic properties and infrared spectrum are investigated using density functional theory including scalar relativistic effects. The complex is compared with the well-known uranocene U(η8-C8H8)2. Despite the broken symmetry, the gain in electrostatic interaction and a significant uranium-CN− orbital interaction is sufficient to stabilize the bent CN− complex with respect to uranocene. The formation of the CN− complex is exothermic justifying the recently experimentally reported compound.

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Acknowledgments

We would like to thank Dr. Michel Ephritikhine for fruitful discussions and a careful reading of the manuscript.This work was granted access to the HPC resources of [CCRT/CINES/IDRIS] under the allocation i2010086146 made by GENCI (Grand Equipement National de Calcul Intensif).

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Authors and Affiliations

  1. Laboratoire des Mécanismes Réactionnels, Département de Chimie, Ecole Polytechnique, CNRS, 91128, Palaiseau Cedex, France

    Carine Clavaguéra

  2. CEA/SACLAY, UMR 3299 CEA/CNRS SIS2M, Laboratoire de chimie de coordination des éléments f, 91191, Gif-sur-Yvette, France

    Jean-Pierre Dognon

Authors
  1. Carine Clavaguéra
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  2. Jean-Pierre Dognon
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Correspondence to Carine Clavaguéra.

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Dedicated to Professor Pekka Pyykkö on the occasion of his 70th birthday and published as part of the Pyykkö Festschrift Issue.

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Clavaguéra, C., Dognon, JP. Theoretical study of the bent U(η8-C8H8)2(CN)− complex. Theor Chem Acc 129, 447–452 (2011). https://doi.org/10.1007/s00214-010-0879-3

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