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Sabino JR, Coppens P. On the choice of d-orbital coordinate system in charge-density studies of low-symmetry transition-metal complexes. Acta Crystallogr A. 2003;59:127-31doi: 10.1107/s0108767302023127.
Sabino, J. R., & Coppens, P. (2003). On the choice of d-orbital coordinate system in charge-density studies of low-symmetry transition-metal complexes. Acta crystallographica. Section A, Foundations of crystallography, 59127-31. https://doi.org/10.1107/s0108767302023127
Sabino, José R, and Coppens, Philip. "On the choice of d-orbital coordinate system in charge-density studies of low-symmetry transition-metal complexes." Acta crystallographica. Section A, Foundations of crystallography vol. 59 (2003): 127-31. doi: https://doi.org/10.1107/s0108767302023127
Sabino JR, Coppens P. On the choice of d-orbital coordinate system in charge-density studies of low-symmetry transition-metal complexes. Acta Crystallogr A. 2003 Mar;59:127-31. doi: 10.1107/s0108767302023127. Epub 2003 Feb 26. PMID: 12604850.
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Acta Crystallogr A. 2003 Mar;59:127-31. doi: 10.1107/s0108767302023127. Epub 2003 Feb 26.

On the choice of d-orbital coordinate system in charge-density studies of low-symmetry transition-metal complexes.

Acta crystallographica. Section A, Foundations of crystallography

José R Sabino, Philip Coppens

Affiliations

  1. Institute of Physics of São Carlos, University of São Paulo, São Carlos, SP, Brazil.

PMID: 12604850 DOI: 10.1107/s0108767302023127

Abstract

The distribution of the d electrons over the corresponding orbitals in transition-metal complexes is a central concept in the theory of metal-ligand bonding. The description requires the assignment of an axis of quantization, which is unambiguous in symmetric environments but not clear-cut in the now commonly encountered case of a low-symmetry coordination environment. As the d-electron population can be derived from accurate diffraction data using the methods of charge-density analysis [HollaDay et al. (1983). Acta Cryst. A39, 377-387], the need for an appropriate procedure is relevant in this area of crystallography. Several criteria for the choice of coordinate system based on the resulting orbital populations are discussed. They are tested on a cobalt atom in a trigonal bipyramidal site and applied to transition-metal sites in Cu(II)-alanyl-valine, and an open zirconocene. The population of the d-orbital cross terms for the different coordinate-system orientations is used to judge the results. In the cases examined, the intuitively most reasonable coordinate system corresponds to the one with smaller value of the sum of the populations of the d-orbital cross terms.

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