{"title":"镍(IV)肟-亚胺配合物氧化巯基乙酸的动力学和机理研究","authors":"S. Bhattacharya, A. Dutta, P. Banerjee","doi":"10.1515/irm-1998-0105","DOIUrl":null,"url":null,"abstract":"Abstract The kinetics of oxidation of thioglycolic acid (H2A) by two nickel(IV) oxime-imine complexes, [NiIV(L1)2]2 + and [NiIV(L2)]2+ (where HL1 and H2L2 are 6-amino-3-methyl-4-azahex-3-ene-2-one oxime and 3,14-dimethyl-4,7,10,13-tetraazahexadeca-3,13- diene-2,15-dione dioxime respectively) were carried out by using stopped-flow technique in the pH range 3.0-8.0. Under pseudo-first-order conditions the reaction follows a general rate law: - (d/dt) [Ni(Lx)] =kobs [Ni(Lx)] = nk [Ni(Lx)] [H2A]T where n is the stoichiometric factor with 0.5 for NiIV → NIII reactions and 1 for each step of Ni IV→ NiIII → NiII biphasic conversions. The evaluation of rate and equilibrium constants of the reactants was achieved by employing suitable computer-fit programs. Both the reactions have been proposed to follow the inner-sphere mechanism through the formation of an associated species involving the sulfur atom of the thiol and the metal center of the oxidant.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"1998-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"2","resultStr":"{\"title\":\"Oxidation of Thioglycolic Acid by Nickel(IV) Oxime-Imine Complexes - A Kinetic and Mechanistic Approach\",\"authors\":\"S. Bhattacharya, A. Dutta, P. Banerjee\",\"doi\":\"10.1515/irm-1998-0105\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Abstract The kinetics of oxidation of thioglycolic acid (H2A) by two nickel(IV) oxime-imine complexes, [NiIV(L1)2]2 + and [NiIV(L2)]2+ (where HL1 and H2L2 are 6-amino-3-methyl-4-azahex-3-ene-2-one oxime and 3,14-dimethyl-4,7,10,13-tetraazahexadeca-3,13- diene-2,15-dione dioxime respectively) were carried out by using stopped-flow technique in the pH range 3.0-8.0. Under pseudo-first-order conditions the reaction follows a general rate law: - (d/dt) [Ni(Lx)] =kobs [Ni(Lx)] = nk [Ni(Lx)] [H2A]T where n is the stoichiometric factor with 0.5 for NiIV → NIII reactions and 1 for each step of Ni IV→ NiIII → NiII biphasic conversions. The evaluation of rate and equilibrium constants of the reactants was achieved by employing suitable computer-fit programs. Both the reactions have been proposed to follow the inner-sphere mechanism through the formation of an associated species involving the sulfur atom of the thiol and the metal center of the oxidant.\",\"PeriodicalId\":8996,\"journal\":{\"name\":\"BioInorganic Reaction Mechanisms\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1998-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"2\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"BioInorganic Reaction Mechanisms\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1515/irm-1998-0105\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"BioInorganic Reaction Mechanisms","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1515/irm-1998-0105","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Oxidation of Thioglycolic Acid by Nickel(IV) Oxime-Imine Complexes - A Kinetic and Mechanistic Approach
Abstract The kinetics of oxidation of thioglycolic acid (H2A) by two nickel(IV) oxime-imine complexes, [NiIV(L1)2]2 + and [NiIV(L2)]2+ (where HL1 and H2L2 are 6-amino-3-methyl-4-azahex-3-ene-2-one oxime and 3,14-dimethyl-4,7,10,13-tetraazahexadeca-3,13- diene-2,15-dione dioxime respectively) were carried out by using stopped-flow technique in the pH range 3.0-8.0. Under pseudo-first-order conditions the reaction follows a general rate law: - (d/dt) [Ni(Lx)] =kobs [Ni(Lx)] = nk [Ni(Lx)] [H2A]T where n is the stoichiometric factor with 0.5 for NiIV → NIII reactions and 1 for each step of Ni IV→ NiIII → NiII biphasic conversions. The evaluation of rate and equilibrium constants of the reactants was achieved by employing suitable computer-fit programs. Both the reactions have been proposed to follow the inner-sphere mechanism through the formation of an associated species involving the sulfur atom of the thiol and the metal center of the oxidant.