GALSBPHIL Frode University of Copenhagen Associate Professor, 助教授
SCHAFFER Claus University of Copenhagen Professor, 教授
KOJIMA Masaaki Okayama University Associate Professor, 理学部, 助教授 (20022725)
柏原 和夫 名古屋大学, 理学部, 助教授 (60004496)
FUJITA Junnosuke Nagoya University Professor, 理学部, 教授 (80004266)
KAZUO Kashiwabara Nagoya University Associate Professor
|Budget Amount *help
¥7,000,000 (Direct Cost: ¥7,000,000)
Fiscal Year 1990: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 1989: ¥3,500,000 (Direct Cost: ¥3,500,000)
1. Fujita, Galsbphil, and their associates prepared a new pair of geometrical isomers of the dichloro-Rh (III) complex with 1, 3-bis (dimethylarsino) propane (dmap), cis- and trans-[RhCl_2 (dmap)_2]^+, and determined the structures by the X-ray diffraction method. The Rh-As distances in the linear As-Rh-As groups are longer by 0.04-0.07 A than those in the linear Cl-Rh-As groups. A little larger lengthening of mutually trans Rh-P bonds (0.05-0.09 A) has been observed for analogous phosphine complexes, A comparison of ligand field spectra of these arsine complexes with those of the corresponding diamine and diphosphine complexes indicates that the spectrochemical series of the 5B (15) group donor atoms is P > As > N.
2. Fujita, Galsbpsil, and their associates also obtained a new dichlor-Ir (III) complex with (2-aminoethyl) dimethylphosphine (edmp), [IrCl_2 (edmp)_2]^+. The complex was found to be trans (Cl, Cl), trans (P, P) isomer by X-ray analysis, in contrast with the selective formation of the trans (Cl, Cl), cis (P, P) isomer for Co (III) and Rh (III).
3. Yamatera and Schaffer completed a joint research on the ligand field of symmetrical, pi-conjugated bidentate ligands parametrized by the angular overlap model (AOM). Bidentates of this type were treated as a new type of ligands characterized by the conjugation of ligator pi* orbitals, which prevents the application of the conventional AOM. The analysis by use of the molecular orbital orientation of the AOM concludes that the e_<pi*> parameter of the conventional AOM has to be replaced by two independent parameters, e_<psi> and e_<chi>, which correspond to in-phase and out-of-phase combinations of ligator pi* orbitals. Two equivalent parametrization schemes, a ligator scheme and a ligand scheme, have been devised. In the latter scheme, the bite angle is implicitly included in the e parameter and the ligand behaves as a non-linearly ligating unidentate ligand. The AOM formalism is retained in both schemes.