QTAIM view of metal–metal bonding in di- and trinuclear disulfido carbonyl clusters

Farrugia, L.J., Evans, C., Senn, H.M. , Hänninen, M.M. and Sillanpaa, R. (2012) QTAIM view of metal–metal bonding in di- and trinuclear disulfido carbonyl clusters. Organometallics, 31(7), pp. 2559-2570. (doi: 10.1021/om2011744)

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Publisher's URL: http://dx.doi.org/10.1021/om2011744


The experimental and theoretical charge densities in the sulfido-bridged cluster compounds Fe<sub>2</sub>(μ-S<sub>2</sub>)(CO)<sub>6</sub>, Fe<sub>3</sub>(μ3-S)<sub>2</sub>(CO)<sub>9</sub>, Mn<sub>2</sub>(μ-S<sub>2</sub>)(μ-CO)(CO)<sub>6</sub>, and Fe<sub>2</sub>(μ-S<sub>2</sub>)(CO)<sub>5</sub>(PPh<sub>3</sub>) have been studied using the quantum theory of atoms in molecules (QTAIM) methodology. High-resolution X-ray diffraction data have been measured for compounds 2–4 at 100 K. The topological analyses show that only in compounds 1 and 4 is there any evidence for metal–metal bonding in terms of the presence of a bond path. For compound 1, the topology of the Fe<sub>2</sub>S<sub>2</sub> cage is highly dependent on the Fe–Fe separation, and the deformation along this vector is an extremely soft mode. The experimentally observed topology for compound 4 is the open “butterfly” topology. The orbital decomposition of the delocalization indices associated with the metal–metal interactions, σ(ΩM–ΩM), implies significant direct Fe–Fe bonding in compounds 1 and 4 and for two of the Fe–Fe vectors in 2 but only a very minor Mn–Mn interaction in compound 3. The crystal structure of 2 shows a small amount (1%) of orientational disorder. As a result, a small degradation of the derived topological parameters is detectable, in comparison with the ordered structures of 3 and 4, and this leads us to discourage any quantitative QTAIM studies on disordered systems.

Item Type:Articles
Glasgow Author(s) Enlighten ID:Farrugia, Dr Louis and Senn, Dr Hans
Authors: Farrugia, L.J., Evans, C., Senn, H.M., Hänninen, M.M., and Sillanpaa, R.
Subjects:Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Organometallics
Publisher:American Chemical Society
ISSN (Online):1520-6041
Published Online:09 February 2012

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