{"title":"顺磁配合物间电子转移的核磁共振研究自交换反应[fe30o (O2CCMe3)6(py)3]+/0 (py =吡啶)动力学","authors":"F. E. Sowrey, C. Macdonald, R. D. Cannon","doi":"10.1039/A801051J","DOIUrl":null,"url":null,"abstract":"The kinetics of the electron transfer self-exchange reaction [Fe3O(O2CCMe3)6(py)3]+ + [Fe3O(O2CCMe3)6(py)3] ⇄ [Fe3O(O2CCMe3)6(py)3] + [Fe3O(O2CCMe3)6(py)3]+ have been measured by NMR line broadening. Both reactants are paramagnetic and it was possible to measure broadening of lines of each component by exchange with the other. In dichloromethane at 23 °C the second-order rate constant is (3.7 ± 0.1) × 104M−1 s−1. The ligand exchange reactions of [Fe3O(O2CCMe3)6(py)3]n+ with pyridine are rapid for the mixed-valence complex (n = 0) but slow for the oxidised complex (n = 1).","PeriodicalId":17286,"journal":{"name":"Journal of the Chemical Society, Faraday Transactions","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"1998-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"14","resultStr":"{\"title\":\"NMR study of electron transfer between paramagnetic complexes Kinetics of the self-exchange reaction [Fe3O(O2CCMe3)6(py)3]+/0 (py = pyridine)\",\"authors\":\"F. E. Sowrey, C. Macdonald, R. D. Cannon\",\"doi\":\"10.1039/A801051J\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The kinetics of the electron transfer self-exchange reaction [Fe3O(O2CCMe3)6(py)3]+ + [Fe3O(O2CCMe3)6(py)3] ⇄ [Fe3O(O2CCMe3)6(py)3] + [Fe3O(O2CCMe3)6(py)3]+ have been measured by NMR line broadening. Both reactants are paramagnetic and it was possible to measure broadening of lines of each component by exchange with the other. In dichloromethane at 23 °C the second-order rate constant is (3.7 ± 0.1) × 104M−1 s−1. The ligand exchange reactions of [Fe3O(O2CCMe3)6(py)3]n+ with pyridine are rapid for the mixed-valence complex (n = 0) but slow for the oxidised complex (n = 1).\",\"PeriodicalId\":17286,\"journal\":{\"name\":\"Journal of the Chemical Society, Faraday Transactions\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1998-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"14\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the Chemical Society, Faraday Transactions\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1039/A801051J\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the Chemical Society, Faraday Transactions","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1039/A801051J","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
NMR study of electron transfer between paramagnetic complexes Kinetics of the self-exchange reaction [Fe3O(O2CCMe3)6(py)3]+/0 (py = pyridine)
The kinetics of the electron transfer self-exchange reaction [Fe3O(O2CCMe3)6(py)3]+ + [Fe3O(O2CCMe3)6(py)3] ⇄ [Fe3O(O2CCMe3)6(py)3] + [Fe3O(O2CCMe3)6(py)3]+ have been measured by NMR line broadening. Both reactants are paramagnetic and it was possible to measure broadening of lines of each component by exchange with the other. In dichloromethane at 23 °C the second-order rate constant is (3.7 ± 0.1) × 104M−1 s−1. The ligand exchange reactions of [Fe3O(O2CCMe3)6(py)3]n+ with pyridine are rapid for the mixed-valence complex (n = 0) but slow for the oxidised complex (n = 1).
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