Research of Molecular Design, Reactivity, and Some Properties for s- and Se-Bridged Polynuclear Complexes

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In this work, we obtained the following results(1)-(3):(1)Three kinds of S-bridged dinuclear complexes, DELTA- and LAMBDA-[CO_2(aet)_3(dien)]^<3+>(aet=2-aminoethanethiolate and dien = diethylenetriamine), DELTA- and LAMBDA-[Co_2(aet)_3(dpt)]^<3+> (dpt = bis(3-aminopropyl)amine)), and DELTA_<LLL>-[CO_2(L-cys-N,S)_3(dien)]^<3+> (L-cys = L-cysteinate), were prepared by the reaction of [Co(aet)_3] or DELTA_<LLL>-[CO(L-cys-N,S)_3]^<3-> with [CoCl_3(dien)] or [CoCl_3(dpt). The isomers were characterized from their absorption, CD, and ^<13>CNMR spectra.(2)The novel mononuclear, dinuclear, and trinuclear cobalt(III) complexes with D-penicillaminate (D-pen), LAMBDA_<DDD>-fac(S)-[Co(D-(pen-N,S)_3]^<3->, LAMBDA_<DDD>-[Co(Co(D-pen-N,S)_3(dien)], LAMDA_<DDD>-[Co{Co(D-pen-N,S)_3(D-pen-N,O,S)]^<2->, and LAMBDA_<DDD>DELTA_<DDD>-[Co{Co(D-pen-N,S)_3}_2]^<3-> were prepared. These complexes were characterized from their electronic absorption, CD, and ^<13>C NMR spectra. These complexes formed selectively … More each one isomer. The stereoselectivity for the D-pen complexes is discussed in comparison with that of the corresponding L-cys ones. the D-pen polynuclear complexes exhibited characteristic absorption spectral behaviors in the visible region. The ^<13>C NMR spectral behaviors for the D-pen complexes are connected with those of the corresponding L-cys ones.(3) The novel T-cage-type Se-bridged polynuclear complexes with 2-aminoethaneselenolate (aese) [{Co(aese)_3}_4Zn_mX]^<n+> (X = O (m,n=4,6) or C1 (m,n=3,5 and 4,7)) and [{Rh(aese)_3}^4Zn_4O]Br_6, have been synthesized. Of these complexes, the spontaneous resolution was recognized for the Co(III) and Rh(III) complexes with the [Zn_4O]^<6+> core. The crystal structure of was determined by the X-ray diffraction method. The four octahedral fac(Se)-[Co(aese)_3] subunits are bound to the tetrahedral [Zn_4O]^<6+> core with the central mu^4-oxygen atom to take to kate a tetrahedral arrangement, giving T symmetrical structure. The chiral configurations are regulated to DELTA or RAMDA for all four fac(Se)-[Co(aele)_3] subunits. The electronic absorption and CD spectral behavior of these complexes are discussed in comparison with those of related mononuclear and linear-type S -bridged trinuclear complexes, and the corresponding cage-type polynuclear complexes. Less