화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.116, No.24, 11014-11019, 1994
An Unusual Type of H...H Interaction - Ir-H...H-O and Ir-H...H-N Hydrogen-Bonding and Its Involvement in Sigma-Bond Metathesis
A series of metal hydride complexes is described (1, 6, and 7) containing X-H...H-Ir (X = O or N) hydrogen bonds. The H...H distance is short, about 1.8 Angstrom, as in the N-H...H-Ir system independently discovered recently (1994) by Ramachandran and Morris, but much shorter than the prior (1990) O-H...H-Ir system of Milstein et al. A J-coupling of 2-4 Hz in the NMR spectrum is often found between H-a and H-b in X-H-a...H-b-Ir. Exchange between H-a and H-b occurs on the NMR time scale, probably via proton transfer to give hydrogen complexes X...-(H-2)-M as intermediates. The interaction activates the Ir-H bond for reactions such as substitution, and cyclometalation. NMR data indicates an H-bond strength of 4.3 +/- 0.8 kcal/mol in one case (7). The species give sigma-bond metathesis reactions and easily lose H-2 to give a cyclometalated derivative, a reaction which is reversible in some cases. Reasons for the formation of a strong H-bond in this case are proposed : the close approach possible for H-a and H-b; the absence of lone pair repulsion; and the high polarizability of the Ir-H bond.