Hydrido diamine ruthenium complexes and their use as hydrogenation and Michael addition catalysts

INOR 440

Robert H. Morris, rmorris@chem.utoronto.ca, Sean E. Clapham, Rongwei Guo, Marco Zimmer-De Iuliis, Nailyn Rasool, and Alan J. Lough. Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON M5S 3H6, Canada
The complexes RuHX(diamine)(PPh3)2 containing 1,2-diamino-2,3-dimethylbutane (tmen) are prepared by reacting the stable amido-hydrido complexes, RuH(NH2CMe2CMe2NH)(PPh3)2 (1) with weak acids, HX (X = H,1 OPh, p-SC6H4OMe, OPPh2, OP(OEt)2, CCPh, NCCHCN, CH(COOMe)2). The X ligand is trans to the hydride. Analogous osmium complexes are also being prepared and studied. RuH(CH(COOMe)2)(tmen)(PPh3)2 (2) has an unusual O-bonded dimethylmalonate ligand. Similar ruthenium complexes with 1,2-diaminocyclohexane (dach) are synthesized by reaction of RuHCl(dach)(PPh3)2 with KOtBu and HX. The effect of X on the catalytic activity of the complexes for the H2-hydrogenation of acetophenone to 1-phenylethanol and the Michael addition of dimethylmalonate to 2-cyclohexen-1-one will be reported. RuH(NCCHCN)(tmen)(PPh3)2 reacts with the Michael acceptor, 2-cyclohexen-1-one to form RuH(NCC(C6H9O)CN)(tmen)(PPh3)2, a trapped Michael adduct that has been crystallographically characterized.

1 Abdur-Rashid, K.; Clapham, S. E.; Hadzovic, A.; Harvey, J. N.; Lough, A. J.; Morris, R. H. J. Am. Chem. Soc. 2002, 124, 15104-15118.

 

Organometallic: Catalysis
9:00 AM-12:00 PM, Monday, 11 September 2006 Moscone Center -- Room 310, Oral

Division of Inorganic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006