|Budget Amount *help
¥1,700,000 (Direct Cost : ¥1,700,000)
Fiscal Year 1993 : ¥400,000 (Direct Cost : ¥400,000)
Fiscal Year 1992 : ¥400,000 (Direct Cost : ¥400,000)
Fiscal Year 1991 : ¥900,000 (Direct Cost : ¥900,000)
The cobalt (III) complexes (alpha, beta-1, and beta-2 [Co(eddp)(en)X, beta-[Co(tndp)(en)X, and alpha-[Co(Me_2eddp)(en)]X) containing diaminodicarboxylates [^-OCOCH_2CH_2NR(CH_2) nNRCH_2CH_2COO^- : eddp(R=H, n=2) ; tndp (R=H, n=3) ; Me_2eddp (R=CH_3, n=2)] as quadridentate ligands and ethylenediamine [NH_2CH_2CH_2NH_2 : en] as a bidentate ligand were newly prepared and optically resolved. The geometrical structures and absolute configurations were determined on the basis of the absorption, CD, C-13 NMR spectral date and the crystallographic date.
The aqueous solution of racemic and optically active complexes were irradiated by a 400W high-pressure mercury lamp (internal irradiating lamp) at ca, 5ﾟC for 40-60 min. The resulted solution were column-chromatographed and the desired complexes containing cobalt(III)-carbon bond were obtained from orange and purple eluates. The C-13 NMR spectra of these orange and purple complexes exhibited characteristic resonance peaks at very high magnetic field (at ca.-5 ppm), which are assigned to the carbanion-carbon coordinated to a cobalt(III) ion.
The geometrical structures and absolute configurations of the optically active complexes containing Co-C bond were determined on the basis of the absorption, CD, C-13 NMR spectral date and the crystallographi date. The photolyses of the optically active LAMBDA-alpha, LAMBDA-beta-1, and LAMBDA-beta-2 [Co(eddp)(en)]X produced stereospecifically Co-C bond isomers having LAMBDA-alpha, DELTA-alpha, and LAMBDA (or DELTA)-beta configurations, respectively, and the photolyses of DELTA-beta-[Co(tndp)(en)]X and LAMBDA-alpha-[Co(Me_2eddp)(en)]X produced LAMBDA (or DELTA)-beta and LAMBDA-alpha Co-C bond isomers, respectively.
The present results suggested that the photodecarboxylation occurred stereospecifically on one of the two carboxy1 groups of the coordinated diaminodicarboxyate.