BioInorganic Reaction Mechanisms最新文献_第2页

Kinetics and Mechanism of Uncatalysed Exchange of Cyanide in Hexacyanoferrate(II) by N-Methylpyrazinium Cation n -甲基吡嗪阳离子在六氰高铁酸盐(II)中非催化交换氰化物的动力学和机理

BioInorganic Reaction Mechanisms Pub Date : 2008-01-01 DOI: 10.1515/IRM.2008.6.4.337

S. Prasad, R. Naik, V. Chand

引用次数: 2

Micellar Effects on Vanadium(V) Oxidation of Lactic Acid in Aqueous Acid Media: A Kinetic Study 乳酸水溶液中钒(V)氧化胶束效应的动力学研究

BioInorganic Reaction Mechanisms Pub Date : 2008-01-01 DOI: 10.1515/IRM.2008.6.4.287

B. Saha

引用次数: 6

A Novel Aspect of Hexacyanoferrate (III)- Iodide Ion Reaction in Acidic Medium 酸性介质中六氰高铁酸盐(III)-碘离子反应的新进展

BioInorganic Reaction Mechanisms Pub Date : 2007-12-01 DOI: 10.1515/IRM.2007.6.3.201

P. Tandon, A. Mehrotra, Manish Srivastava, S. Singh, Satpal Singh

引用次数: 0

Investigation of Copper(II) – Thiosulfate Reaction Kinetics 铜(II) -硫代硫酸盐反应动力学研究

BioInorganic Reaction Mechanisms Pub Date : 2007-01-01 DOI: 10.1515/IRM.2007.6.3.239

M. Ungureșan, G. Niac

引用次数: 3

Kinetics andMechanism of Adducts Formation of Tetraaza Cobalt (II) Complex with Organic Bases in Dimethylsulfoxide Solvent 四氮钴(II)与有机碱配合物在二甲亚砜溶剂中形成加合物的动力学和机理

BioInorganic Reaction Mechanisms Pub Date : 2007-01-01 DOI: 10.1515/IRM.2007.6.3.193

M. Asadi, Z. Asadi

引用次数: 1

Inner-Sphere Oxidation of Binary and Ternary Uridine Chromium(III) Complexes Involving Aspartate by Periodate 含天冬氨酸的二元和三元尿苷铬(III)配合物的高碘酸盐球内氧化

BioInorganic Reaction Mechanisms Pub Date : 2007-01-01 DOI: 10.1515/IRM.2007.6.3.247

Eman S. H. Khaled

引用次数: 9

The Kinetics and Mechanism of Oxidation of Triethylenetetraaminehexaacetatocobaltate(II) Complex by Periodate Ion in AqueousMedium 高碘酸离子在水介质中氧化三乙四胺六乙酸钴酸盐(II)配合物的动力学及机理

BioInorganic Reaction Mechanisms Pub Date : 2007-01-01 DOI: 10.1515/IRM.2007.6.3.185

R. Naik, A. Srivastava, A. Verma, S. Yadav, Ruchi Singh, S. Prasad

{"title":"The Kinetics and Mechanism of Oxidation of Triethylenetetraaminehexaacetatocobaltate(II) Complex by Periodate Ion in AqueousMedium","authors":"R. Naik, A. Srivastava, A. Verma, S. Yadav, Ruchi Singh, S. Prasad","doi":"10.1515/IRM.2007.6.3.185","DOIUrl":"https://doi.org/10.1515/IRM.2007.6.3.185","url":null,"abstract":"The kinetics and mechanism of oxidation of [Co(II)TTHA]4- (where TTHA = Triehylenetetraaminehexaaceticacid) by periodate ion has been studied in aqueous acidic medium. The reaction has been investigated spectrophotometrically at λmn = 550 nm under pseudo first- order condition by taking large excess of oxidant, [IO4-] at pH = 4.0 + 0.02, 1 = 0.1 M (CH3COONa + Na NO3) and at three different temperatures viz 150 C, 200 C and 250 C. The electron transfer reaction between [Co(II)TTHA]4- and , [IO4-] obeys inner- sphere reaction pathway through the formation of long lived intermediate complex which eventually get converted into a corresponding [Co(III)TTHA]3- complex as final reaction product. The experimental observations have shown that the reaction exhibit first- order dependence in [Co(II)TTHA]4- . The variation of pseudo- first- order rate constant (Kabc) with [IO4-] keeping other reaction variables fixed at constant value is found to obey the following empirical equation. Kabc = a[IO4-]2/b + c[IO4-] This rate law is consistent with a three step mechanistic scheme. The values of (Kabc) are almost invariant with increasing pH and attributed due to the reaction of deprotonated form of [Co(II)TTHA]4- complex and [IO4-] in the whole pH region. Eyring’s equations has been used to calculate the activation parameters and found to be ∆H* = 16.63 KJ mole-1 ; ∆S* = -214.00 JK-1 mole-1. These values are consistent with three step mechanistic scheme as proposed.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"34 1","pages":"185 - 192"},"PeriodicalIF":0.0,"publicationDate":"2007-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76919538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Kinetic andMechanistic Study of 2,2'- Bipyridyl the Catalyzed Chromium(VI) Oxidation of Lactic Acid 2,2′-联吡啶基催化铬(VI)氧化乳酸的动力学与机理研究

BioInorganic Reaction Mechanisms Pub Date : 2007-01-01 DOI: 10.1515/IRM.2007.6.3.225

J. Shan, L. Fan, S. Huo, H. M. Liu, S. Shen

引用次数: 0

Kinetic and Mechanistic Studies of the Interaction of Hydroxopentaaquarhodium(III) Ion with Cyanocobalamin 羟基戊四氢钠(III)离子与氰钴胺相互作用的动力学和机理研究

BioInorganic Reaction Mechanisms Pub Date : 2007-01-01 DOI: 10.1515/IRM.2007.6.3.211

G. C. Dash, B. Dash, P. K. Satpathy, P. Mohanty

引用次数: 0

Kinetics of the Reaction of Mer-Tris(Picolinato) Iron(III) with Hydrogen Peroxide in Pyridine: Role of Hydroxyl Radicals in Subsequent Catalytic Oxygenation of Cyclohexane to the Ketone. 吡啶中甲-三吡啶(Picolinato)铁(III)与过氧化氢反应动力学:羟基自由基在环己烷随后催化氧化生成酮中的作用

BioInorganic Reaction Mechanisms Pub Date : 2007-01-01 DOI: 10.1515/IRM.2007.6.3.169

D. Richens, S. Jain, Andrew C. Gale

{"title":"Kinetics of the Reaction of Mer-Tris(Picolinato) Iron(III) with Hydrogen Peroxide in Pyridine: Role of Hydroxyl Radicals in Subsequent Catalytic Oxygenation of Cyclohexane to the Ketone.","authors":"D. Richens, S. Jain, Andrew C. Gale","doi":"10.1515/IRM.2007.6.3.169","DOIUrl":"https://doi.org/10.1515/IRM.2007.6.3.169","url":null,"abstract":"Reaction of pale-green high spin mer-tris(picolinato)iron(III) with t-butylhydroperoxide in pyridine gives rise to an EPR signal for the t-butylperoxyl radical via a short lived purple intermediate which itself decays eventually to a yellow-brown high spin iron(III) product. The kinetics of the corresponding reaction with hydrogen peroxide have been studied in regard to the dependence of the hydrogen peroxide and picolinic acid concentration on the rate of the initial stages. The results support two rate-determining initial steps (minutes) involving the formation of a short lived purple high spin hydroperoxoor tbutylperoxoiron(III) intermediate (λmax = 530 nm, ε ~ 1,000 dm3 mol-1 cm-1 for the hydroperoxo species) via pre-equilibrium loss of one picolinic acid which then undergoes homolytic Fe-O bond cleavage to give iron(II) and hydroperoxyl (t-butylperoxyl) radical resulting in eventual formation of deep yellow-brown solution which undergoes further complex UV-visible changes over a period of several hours. During this latter timescale these solutions are able to carry out Gif-type catalytic oxygenation of cyclohexane to cyclohexanone in the presence of H2O2 (or O2/pyH/Zn powder) a process which however is completely inhibited in the presence of small amounts of dimethylsulfoxide, an efficient scavenger of the hydroxyl radical. Bis(picolinato)copper(II) was found to be a poor oxygenation catalyst, a finding consistent with its inability to generate the hydroxyl radical via Cu(I) under the same conditions. These results confirm that generation of hydroxyl radicals (via reaction of H2O2 with iron(II) or any other suitably reactive lower valent state) is central to the oxygenation chemistry carried out by these solutions.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"92 1","pages":"169 - 183"},"PeriodicalIF":0.0,"publicationDate":"2007-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79159215","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 3