Assignment and conformational investigation of asymmetric phenylindenylidene ruthenium complexes bearing N,O‐bidentate ligands

The NMR conformational study of three asymmetric phenylindenylidene ruthenium complexes 4.1–4.3, is presented. Complete ¹H and ¹³C assignments could be obtained for 4.1–4.3 in benzene solution from multiple 2D homonuclear and heteronuclear NMR techniques. Our NMR analysis shows that each complex exists as a 55:45 mixture of two rotational isomers in slow exchange on the NMR chemical shift timescale. They are shown to be related by a 180° flip of the indenylidene ligand along the Ru?CR bond. Both rotational isomers can be discriminated by means of NOEs contacts between the various ligands coordinating to the Ru. By matching these stereospecific assignments to the chemical shift, a chemical shift based fingerprint of the isomers that may allow straightforward assignment of future asymmetric phenylindenylidene ruthenium complexes is proposed. Copyright © 2010 John Wiley & Sons, Ltd.