This contribution will describe how experiment and theory can combine to provide insight into fundamental bond activation processes at Ru-NHC complexes. Thus, in the presence of imidazolium chloride, cyclometalated 1  undergoes C-N bond cleavage with loss of propene to give 2  . Labelling and computational studies suggest the involvement of an agostic intermediate and a novel mode of base-induced C-H bond cleavage. Similarly, 16e Ru-NHC complexes of type 3  can effect the catalytic hydrodefluorination of fluoroaromatics. With pentafluorobenzene this proceeds with an unusual ortho regioselectivity. Calculations suggest that a novel nucleophilic attack mechanism, whereby a hydride ligand attacks the fluoraromatic. The presence of bulky N-aryl substituents is thought to control the selectivity.

Combined computational and experimental studies of C-H, C-N and C-F bond activation at ruthenium N-heterocyclic carbene complexes

244th National Meeting (2012)

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