PHOTOCHEMISTRY OF COBALT(III) COMPLEXES .1. OPTICALLY-ACTIVE COBALT(III) COMPLEXES CONTAINING CO-C BOND PREPARED BY PHOTODECARBOXYLATION OFAMINO CARBOXYLATO COMPLEXES

Some cobalt(III) complexes with Co-C sigma-bond have been prepared by photodecarboxylation reactions of the complexes containing ethylenedia mine-N,N'-dipropionate (eddp) or its analogs. The crystal structure of alpha-[Co(Me(2)eedmp-C,N,N',O)(en)](+) (Me(2)eedmp: (CH2CH2N)-C--(CH3 )(CH2)(2)N(CH3)(CH2)(2)COO-), which is the photolysis product of alpha -[Co(Me(2)eddp)(en)](+) (Me(2)eddp: {CH2N(CH3)(CH2)(2)COO-}(2)), was d etermined by the X-ray diffraction method. The crystal is monoclinic, space group P2(1)/n, a=9.013(2), b=13.420(1), c=14.754(4) Angstrom, be ta=92.75(1)degrees, V=1782.5(6) Angstrom(3), Z=4, and R=0.038. The coo rdination of C atom to Co center results in elongation of the Co-O bon d located in the trans position of the C atom, compared with usual Co- O bonds. The photolysis products of optically active isomers (Lambda-a lpha, Lambda-beta(1), and Lambda-beta(2)) of [Co(eddp)(en)](+) were st udied on the basis of the absorption, CD, and C-13 NMR spectral data. The photolysis of Lambda-beta(1) provided Delta-alpha-[Co(eedmp-C,N,N' ,O)(en)](+) (eedmp; (CH2CH2NH)-C--(CH2)(2)NH(CH2)(2)COO-), while the p hotolysis of Lambda-beta(2), which is a conformational diastereomer of Lambda-beta(1), provided (-)(543)(CD)-beta-[Co(edmp-C,N, N',O)(en)]() (major product) and Lambda-alpha-[Co(eedmp-C,N,N',O)(en)](+). Optica lly active (+)(553)(CD)-beta-[Co(etnmp-C,N,N',O)(en)](+) (etnmp: (CH2C H2NH)-C--(CH2)(3)NH(CH2)(2)COO-) was obtained by the photolysis of Del ta-(-)(505)(CD)-beta-[Co(tndp)(en)](+) (tndp: CH2{CH2NH(CH2)(2)COO-}2) .