Part I: Generating Ti(III) species through Ti-O bond homolysis: Thermodynamics, kinetics, and applications. Part II: Photo- and thermochemical activations of small molecules

AEI 55

Kuo-Wei Huang, Chemistry Department, Brookhaven National Laboratory, Bldg. 555, Upton, NY 11973
I: A series of novel titanium nitroxide complexes were prepared. Direct measurements of the rate of Ti-O bond homolysis gave an upper-limit of the Ti-O bond dissociation energies of 25 kcal/mole, which constitutes the weakest Ti-O bonds known for neutral complexes. Thermolysis of the titanocene TEMPO complexes in the presence of epoxides leads to the Cp2Ti(III)Cl-mediated ring-opening of the epoxide followed by trapping by the nitroxyl radical. II: Experimental and DFT computational studies on (a) PCP-pincer Rh complex mediated hydrogenation of CO2 to give Rh-CO and water and (b) carbon-to-metal H-Atom transfer reaction and a special C-H bond activation process involving the addition of the Os radical into the cyclopentadienyl ligand will be reported. The work in II was carried out at BNL under contract DE-AC02-98CH10886 with the US Department of Energy.