CHARACTERIZATION OF PHOTOREACTION PRODUCTS AND PHOTOREACTION MECHANISM

光反应产物的表征及光反应机制

• 批准号: 03640521
• 负责人: YASUI Takaji
• 金额: $ 1.09万
• 依托单位: KOCHI UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03640521/
• 关键词: COBALT(III) COMPLEX; DIAMINODICARBOXYLIC ACID COMPLEX; OPTICALLY ACTIVE COMPLEX; PYOTOLYSIS; CARBON-13 NMR; CIRCULAR DICHROSIM; X-RAY ANALYSIS; ジアミノカルボン酸錯体; 円偏向二色性; アミノカルボン酸錯体; コバルト錯体の立体化学; CDスペクトルと絶対配置; 炭素核NMR; コバルト錯体の光反応; コバルト-炭素結合錯体; コバル

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.

钴（iii）复合物（Alpha，beta-1和beta-2 [Co（eddp）（en）X，beta- [co（tndp）（en）x和alpha- [co（me_2eddp）（en）x），含有含量二氨基辅助辅酶EDDP（r = h，n = 2）; tndp（r = h，n = 3）; ME_2EDDP（r = CH_3，n = 2）]作为鸟类配体的二次配体和乙二胺[NH_2CH_2CH_2NH_2：en]作为鸟类配体是新准备并在光学上解决的。根据抽象，CD，C-13 NMR光谱日期和晶体学日期确定几何结构和绝对构型。在CA上通过400W高压汞灯（内部辐照灯）辐射了射流和光学活性复合物的水溶液，在5 c，5°C，持续40-60分钟。将所得的溶液进行柱状晶状体仪，并从橙色和紫色的洗脱液中获得含有钴（III） - 碳键的所需络合物。 The C-13 NMR spectra of these orange and purple complexes exposed characteristic resonance peaks at very high magnetic field (at ca.-5 ppm), which are assigned to the carbonion-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晶体学日期。光学活性的lambda-alpha，lambda-beta-1和lambda-beta-2 [Co（eddp）（en）] x产生具有lambda-alpha，delta-alpha，delta-alpha和lambda（or delta）-beta的photolys和phothurys和phothate和phothate和phothate and and and and phothate y phothate and phothate y和phothate y和phothate x x产生的立体特异性Co-C键。 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 stereospecified on one of the two carboxy1 groups of the coordinated二氨基二羧酸酯。

项目成果

Hiroshi Kawaguchi, Noboru Maruyama, Tomoharu Ama, and Takaji Yasui: "The Isomerism of the (Ethylenediamine-N,N'-dipropionato)(enthylenediamine) cobalt(III) Ion and its Stereo-selective Isomerization reaction." Bull, Chem.Soc.Jpn.65(1). 175-179 (1992)

Hiroshi Kawaguchi、Noboru Maruyama、Tomoharu Ama 和 Takaji Yasui：“(乙二胺-N,N-二丙酸)(乙二胺)钴(III)离子的异构现象及其立体选择性异构化反应。”

T.Ama,N.Hasegawa,H.Kawaguchi,and T.Yasui: "An optically active cobalt(III)complex containing CoーC bond prepared by the photolysis of optically active(ethylenediamine)(ethylenediaminen,N'ーdipropionato)cobalt(III)complex ion." Chemistry Letters(Chem.Lett.).

T.Ama、N.Hasekawa、H.Kawaguchi 和 T.Yasui：“通过光解光学活性（乙二胺）（乙二胺，N-二丙酸）钴制备的含有 Co-C 键的光学活性钴（III）络合物(III)络离子。”化学快报(Chem.Lett.)。

Tomoharu Ama: "An optically active cobalt(III) complex containing Co-C bond prepared by the photolysis of optically active (ethylenedi-amine)(ethylenediamine-N,N'-dipropionato) cobalt(III) complex ion." Chemistry Letter. 1991. 1543-1546 (1991)

Tomoharu Ama：“通过光解光学活性（乙二胺）（乙二胺-N,N-二丙酸根）钴（III）络合物离子制备的含有 Co-C 键的光学活性钴（III）络合物。”

Hiroshi Kawaguchi: "The isomerism of the (ethylenediamine-N,N'-dipropionato)-(ethylenediamine) cobalt(III) ion and its stereoselective isomerization reaction." Bulletin Chemical Society of Japan. 65. 175-179 (1992)

Hiroshi Kawaguchi：“(乙二胺-N,N-二丙酸)-(乙二胺)钴(III)离子的异构现象及其立体选择性异构化反应。”