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Royal Society of Chemistry, Chemical Science, 3(6), p. 1895-1904, 2015

DOI: 10.1039/c4sc03264k

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What can NMR spectroscopy of selenoureas and phosphinidenes teach us about the π-accepting abilities of N-heterocyclic carbenes?

Journal article published in 2015 by Steve Nolan ORCID, Sai V. C. Vummaleti, David James Nelson ORCID, Albert Poater, Adrián Gómez-Suárez ORCID, David Bradford Cordes, Alexandra M. Z. Slawin, Luigi Cavallo, Adrian Gomez Suarez
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

The electronic nature of the interaction of NHCs with metal centres is of interest when exploring their properties, how these properties influence those of metal complexes, and how these properties might depend on ligand structure. Selenourea and phosphinidene complexes have been proposed to allow the measurement of the [small pi]-accepting ability of NHCs, independent of their [sigma]-donating ability. Herein, the synthesis and characterisation of a range of selenoureas derived from imidazol-2-ylidenes, 4,5-dihydroimidazol-2-ylidenes and triazol-2-ylidenes are documented. Computational studies are used to explore the link between the shielding of the selenium centre and the electronic properties of the NHCs. Results show that [small delta]Se is correlated to the energy gap between a filled lone pair orbital on Se and the empty [small pi]* orbital corresponding to the Se-NHC bond. Bond energy decomposition analysis indicated that there is no correlation between the orbital [sigma]-contribution to bondi