Experimental charge density analysis of a gallium(I) N-heterocyclic carbene analogue

Inorg Chem. 2011 Sep 5;50(17):8418-26. doi: 10.1021/ic2009946. Epub 2011 Aug 2.

Abstract

The experimental electron density of the only known example of a four-membered Ga(I) N-heterocyclic carbene analogue has been determined by multipole modeling of 90 K X-ray diffraction data and compared to theoretical data. In order to obtain a satisfactory model, it is necessary to modify the radial dependency of the core electrons of Ga using two separate scaling parameters for s,p- and d-electrons. Evidence for significant lone-pair density on Ga is found in the electron density and derived properties despite the partial positive charge of this atom. Static deformation density and molecular electrostatic potential clearly show a directional lone pair on Ga, whereas the Laplacian of the total electron density does not; this feature is, however, present in the Laplacian of the valence-only density. The Ga center also acts as an acceptor in four intramolecular C-H···Ga contacts, whose nature is probed by density properties. Substantial covalent character is apparent in the Ga-N bonds, but no sign of donation from filled N p-orbitals to empty Ga p-orbitals is found, whereas π-delocalization over the organic ligand is evident. This study highlights the utility of experimental charge density analysis as a technique to investigate the unusual bonding and electronic characteristics of low oxidation state/low coordinate p-block complexes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Gallium / chemistry*
  • Heterocyclic Compounds / chemistry*
  • Methane / analogs & derivatives*
  • Methane / chemistry
  • Models, Molecular
  • Organometallic Compounds / chemistry*
  • Quantum Theory*

Substances

  • Heterocyclic Compounds
  • Organometallic Compounds
  • carbene
  • Gallium
  • Methane