Unexpected interactions for piano-stool carbene complexes

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A team of researchers from France, Spain and Russia have put forward a case to explain a counter-intuitive conformation of manganese alkylalkoxycarbene complexes.

Using molecular orbitals, it is predicted that such complexes adopt a vertical coordination mode. This is largely the case – although one exception reported by Landman et al. earlier this year (see here) prompted the team to investigate what really is going on…

Coordination modes of carbene ligands in piano-stool complexes

Using a combination of DFT calculations and XRD analysis, Lugan et al. confirm that non-covalent interligand interactions between the alkyl substituents on the carbene and the carbon monoxide ligand (C-HC≡O) are responsible for these complexes adopting the unexpected horizontal coordination mode. Although such an interaction is weak, it goes to show that its enough to influence geometry.

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On the incidence of non-covalent intramolecular interligand interactions on the conformation of carbene complexes: a case study
Noël Lugan, Israel Fernández, Rémy Brousses, Dmitry A. Valyaev, Guy Lavigne and Nikolai A. Ustynyuk
Dalton Trans., 2013, Advance Article

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