Preparation, Reactivity, and Stereochemistry of Cobalt(III) Complexes with Sulfur- or Selenium-containing Peptide

钴(III)与含硫或含硒肽配合物的制备、反应性和立体化学

• 批准号: 60470043
• 负责人: HIDAKA Jinsai
• 金额: $ 3.58万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1986
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-60470043/
• 关键词: cobalt(III) complexes; stereochemistry; sulfur-containing ligand; 不斉配位硫黄原子; 立体化学; コバルト【III】錯体; 含硫および含セレン有機配位子

In this work, we obtained the following results (1)-(5):1) The cobalt(III) complexes with sexidentate ligands, S,S'-ethylenebis(L-homocysteinate) and S,S'-trimethylenebis(L-homocysteinate), were prepared and chromatographically separated into two geometrical isomers. All isomers were characterized by their electronic absorption, CD, and NMR spectra, and their stereo- and spectrochemical features were investigated.2) Each of the two isomers of bis[[tris(L-cysteinato-N,S)cobaltate(III)-<mu>-S,<mu>-S', <mu>S"]] cobaltate(III) was selectively prepared by the reaction of -fac(S)-tris(L-cysteinato-N,S) cobaltate(III) with Co(II) or Co(III). The crystal structure of one isomer was established by the X-ray diffraction study. The absolute configuration of the two [[Co(L-cys-N,S)3]] moieties and the siz sulfur donor atoms were determined. The electronic absorption, CD, and NMR spectra of the two isomers were discussed in relation to their geometrical and absolute configurations.3) The cobalt(III … More ) complex with D- and/or L-selenomethioninate was prepared and separated into the five geometrical isomers. For the four isomers, the optical resolutions were achieved by the column chromatographic method. For the trans(N) and cis,cis,cis isomers which exhibited the electronic absorption, CD, and NMR spectral changes with time in an agueous solution, and inversion on the asymmetric selenium donor atom was investigated by the spectrophotometric method. Their CD spectra were also discussed in relation to the absolute configuration of the asymmetric selenium donor atom.4) The cobalt(III) complexes with 1,3-propanedithiolate and 1,3-propanedisulfinate were prepared and resolved. The crystal structure of one isomer was established by the X-ray diffraction study. The absolute configurations of their isomers were discussed in relation to the CD spectral behavior in the sulfur-to-metal charge transfer and d-d transistion band regions.5) The cobalt(III) complexes with dipeptides, L-methionyl-glycine and glycyl-L-methionine, were prepared and they were characterized by their electronic absorption, CD, and NMR spectra. The stereochemical properties were discussed. Less

1）合成了六齿配体S，S '-亚乙基双（L-同型半胱氨酸）和S，S'-三亚甲基双（L-同型半胱氨酸）钴（III）配合物，并通过色谱分离得到两种几何异构体。通过电子吸收光谱、圆二色谱和核磁共振谱对所有异构体进行了表征，并研究了它们的立体化学和光谱化学特征。2）通过-fac（S）-tris（L-cysteinato-N，S）coolate（III<mu><mu><mu>）与Co（II）或Co（III）反应，选择性地制备了双[[tris（L-cysteinato-N，S）coolate（III）- -S，-S '，S”]]钴（III）酸盐的两种异构体。通过X射线衍射研究确定了一种异构体的晶体结构。确定了两个[[Co（L-cys-N，S）3]]的绝对构型和硫给体原子的大小。讨论了这两种异构体的电子吸收光谱、圆二色性光谱和核磁共振谱与它们的几何构型和绝对构型的关系 ...更多信息 ）与D-和/或L-硒代甲硫氨酸的络合物，并将其分离为五种几何异构体。对于四种异构体，通过柱色谱方法实现了光学拆分。对于反式（N）和顺式、顺式、顺式异构体，用分光光度法研究了它们在水溶液中的电子吸收、圆二色性和核磁共振谱随时间的变化，以及在不对称硒给体原子上的反转。并讨论了它们的圆二色性光谱与硒原子绝对构型的关系。4）合成了1，3-丙二硫醇钴（III）配合物和1，3-丙二亚磺酸钴（III）配合物。通过X射线衍射研究确定了一种异构体的晶体结构。5）合成了二肽-L-甲硫氨酰-甘氨酸和甘氨酰-L-甲硫氨酸钴（III）配合物，并通过电子吸收光谱、圆二色性光谱和核磁共振谱对配合物进行了表征。讨论了其立体化学性质。少

项目成果

日高人才: Bull.Chem.Soc.Jpn.,. 59. 3859-3864 (1986)

日高仁：Bull.Chem.Soc.Jpn.，59. 3859-3864 (1986)

Jinsai Hidaka: "Preparation, Stereochemistry, and CD Spectra of Cobalt(III) Complexes with 1,3- Propanedithiolate and 1,3-Propanedisulfinate" Bull. Chem. Soc. Jpn.,.

Jinsai Hidaka：“钴 (III) 与 1,3- 丙二硫醇盐和 1,3-丙二亚磺酸盐配合物的制备、立体化学和 CD 光谱”公报。

日高人才: Bull.Chem.Soc.Jpn.,. 59. 1145-1150 (1986)

日高仁：Bull.Chem.Soc.Jpn.，59. 1145-1150 (1986)

日高人才: Bull. Chem. Soc. Jpn.,. 59. 3859-3864 (1986)

日高仁：公报。，59。3859-3864（1986）

Jinsai Hidaka: "S-Bridged Polynuclear Complexes.I. Selective Formation and Crystal Structure of (+)^CD_- Bis[[tris(L-cysteinato-N,S)cobaltate(III)-<mu>-S,<mu>-S',<mu>-S'']]cobalt (III) Nitrate Pentahydrate" Bull. Chem. Soc. Jpn.,. 59. 3859-3864 (1986)

Jinsai Hidaka：“S-桥多核配合物。I. ( )^CD_- Bis[[tris(L-cysteinato-N,S)cobaltate(III)-<mu>-S,<mu> 的选择性形成和晶体结构