Formation of [Ru(NHC)4(eta(2)-O2)H]+: an unusual, high frequency hydride chemical shift and facile, reversible coordination of O2

L Jonas L Häller; Elena Mas-Marzá; Aitor Moreno; John P Lowe; Stuart A Macgregor; Mary F Mahon; Paul S Pregosin; Michael K Whittlesey

doi:10.1021/ja9039345

Formation of [Ru(NHC)4(eta(2)-O2)H]+: an unusual, high frequency hydride chemical shift and facile, reversible coordination of O2

J Am Chem Soc. 2009 Jul 22;131(28):9618-9. doi: 10.1021/ja9039345.

Authors

L Jonas L Häller¹, Elena Mas-Marzá, Aitor Moreno, John P Lowe, Stuart A Macgregor, Mary F Mahon, Paul S Pregosin, Michael K Whittlesey

Affiliation

¹ School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, UK.

PMID: 19601678
DOI: 10.1021/ja9039345

Abstract

Reaction of the purple tetrakiscarbene ruthenium cation [Ru(I(i)Pr(2)Me(2))(4)H](+) (1, I(i)Pr(2)Me(2) = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) with oxygen affords the pink eta(2)-O(2) hydride species [Ru(I(i)Pr(2)Me(2))(4)(eta(2)-O(2))H](+) (2). 2 displays (i) a very facile, reversible O(2) coordination and (ii) an unexpectedly positive hydride chemical shift, and both these features can be predicted and explained by density functional theory (DFT) calculations.