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Kinetic and Mechanistic Study of the Interaction Between cis-[Pt(N-N)(H2O)2](ClO4)2 (N-N = ethylenediamine or N,N′-dimethylethylenediamine) and L-glutamic Acid in Aqueous Medium 顺式-[Pt(N-N)(H2O)2](ClO4)2 (N-N =乙二胺或N,N ' -二甲基乙二胺)与l -谷氨酸相互作用的动力学和机理研究
Pub Date : 2005-01-01 DOI: 10.1515/IRM.2005.5.3.173
S. K. Bera, Swapan K. Chandra, G. S. De
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引用次数: 0
Kinetic Study of the Reversible Hydroxide Addition Reaction to a Hexafluoro-2,4-pentanedionato Chelate on a Cobalt(III) Complex 钴(III)配合物上六氟-2,4-戊二酮螯合物可逆氢氧加成反应动力学研究
Pub Date : 2005-01-01 DOI: 10.1515/IRM.2005.5.3.213
Y. Kitamura, Y. Sasaki, Hiroshi Tanaka
*Corresponding author. kitamura@chem.sci.ehime-u.ac.jp † The abbreviations for ligands are: Hhfac = hexafluoro-2,4-pentanedione; MeNH2 = methylamine; EtNH2 = ethylamine; en = ethylenediamine; tn = 1,3-propanediamine; trien = 1,8-diamino-3,6-diazaoctane; tren = 2,2’,2”-triaminotriethylamine; trpn = 3,3’,3”triaminotripropylamine; cyclam = 1,4,8,11-tetraazacyclotetradecane; dien = diethylenetriamine; H(i-dtma) = N,N-bis(2-aminoethyl)glycine; H(5-dptma) = N,N-bis(3-aminopropyl)glycine; H2(edda) = ethylenediamine-N,N’-diacetic acid; H2(aeida) = N-(2-aminoethyl)-N(carboxymethyl)glycine; and H3(nta) = nitrilotriacetic acid. Inorganic Reaction Mechanisims, Vol. 5, pp. 213-230 © 2005 Old City Publishing, Inc. Reprints available directly from the publisher Published by license under the OCP Science imprint, Photocopying permitted by license only a member of the Old City Publishing Group.
*通讯作者。kitamura@chem.sci.ehime-u.ac.jp†配体的缩写是:Hhfac =六氟-2,4-戊二酮;MeNH2 =甲胺;乙胺;乙二胺;Tn = 1,3-丙二胺;三烯= 1,8-二氨基-3,6-重氮辛烷;Tren = 2,2 ',2 " -三胺三乙胺;TRPN = 3,3 ',3 "三胺三丙胺;Cyclam = 1,4,8,11-四氮杂环十四烷;二乙烯三胺;H(i-dtma) = N,N-双(2-氨基乙基)甘氨酸;H(5-dptma) = N,N-二(3-氨基丙基)甘氨酸;H2(edda) =乙二胺-N,N ' -二乙酸;H2(aeida) = N-(2-氨基乙基)-N(羧甲基)甘氨酸;H3(nta) =硝基三乙酸。无机反应机理,第5卷,第213-230页©2005老城出版股份有限公司。可直接从出版商处获得重印,在OCP科学印记下通过许可出版,仅允许旧城出版集团成员的许可复印。
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引用次数: 0
Kinetics of the Reduction of Colloidal MnO2 by Citric Acid in the Absence and Presence of Ionic and Non-ionic Surfactants 柠檬酸在不存在和不存在离子和非离子表面活性剂的情况下还原胶体MnO2的动力学
Pub Date : 2005-01-01 DOI: 10.1515/IRM.2005.5.3.151
Kabir-ud-din, S. Iqubal, Z. Khan
Perez-Benito and his coworkers [1] found first time quantitatively that water soluble colloidal manganese dioxide, prepared from reduction of aqueous potassium permanganate by sodium thiosulphate under neutral condition [2,3], was perfectly transparent and stable for several months. Manganese dioxide (as aqueous suspension) has been used as an oxidizing [4-7] and catalytic [8,9] agent of inorganic/organic compounds. The transparent sols of manganese dioxide too are of importance due to their involvement as active autocatalysts in many permanganate oxidations [10-12]. Surfactants are referred to as amphiphilic, amphipathic, heteropolar or polar/nonpolar compounds due to the characteristic of possessing distinct hydrophobic (water-repelling) and hydrophilic (water-loving) regions in their molecules. The interest in using surfactants as reaction media is that they affect rates, products and, in some cases, stereochemistry of the reactions [13-15]. Studies of chemical reactions in micellar media could provide understanding even about the reactions taking place at Inorganic Reaction Mechanisims, Vol. 5, pp. 151-166 © 2005 Old City Publishing, Inc. Reprints available directly from the publisher Published by license under the OCP Science imprint, Photocopying permitted by license only a member of the Old City Publishing Group.
Perez-Benito等人[1]首次定量地发现,在中性条件下用硫硫酸钠还原高锰酸钾制备的水溶性胶体二氧化锰[2,3]具有完全透明且稳定数月的特性。二氧化锰(作为水悬浮液)已被用作无机/有机化合物的氧化剂[4-7]和催化剂[8,9]。二氧化锰的透明溶胶也很重要,因为它们在许多高锰酸盐氧化中作为活性自催化剂参与[10-12]。由于表面活性剂分子中具有不同的疏水(疏水)和亲水(亲水)区域,因此表面活性剂被称为两亲、两亲、异极性或极性/非极性化合物。使用表面活性剂作为反应介质的有趣之处在于它们会影响反应的速率、产物,在某些情况下还会影响反应的立体化学[13-15]。胶束介质中化学反应的研究甚至可以提供对发生的反应的理解。《无机反应机理》,第五卷,第151-166页©2005 Old City Publishing, Inc。可直接从出版商处获得重印,在OCP科学印记下通过许可出版,仅允许旧城出版集团成员的许可复印。
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引用次数: 19
Mechanistic Studies of the Reaction between Thioglycolic Acid and Chromium(VI): Substitution, Isomerisation, and Electron Transfer 巯基乙酸与铬(VI)反应的机理研究:取代、异构化和电子转移
Pub Date : 2005-01-01 DOI: 10.1515/IRM.2005.5.3.197
Dwight C. Ramdon, D. Dixon, T. Dasgupta
Thioglycolic Acid, H2TGA, containing a reactive sulphydryl group, has been shown to reduce Cr(VI). The experimental conditions were [Cr(VI)]T = 0.20 mM, [TGA]T = 22 – 100 mM, 15.0 ≤ T ≤ 30.0 °C, 2.66 ≤ pH ≤ 4.66 (TGA self-buffer) or 2.74 ≤ pH ≤ 6.05 (citric acid-phosphate) at a constant ionic strength of 0.50 M (NaClO4). The reaction was studied using rapid scanning stopped-flow spectrophotometry at λ = 425 nm. The kinetics of the reaction showed distinct spectral evidence for the formation of an intermediate that was subsequently followed by a slower, bimolecular redox process leading to the formation of the final products. Based on the analysis of the experimental data, the formation of the intermediate involved the conversion of an O-bonded Cr(VI)-thioglycolate intermediate, O3CrOC(O)CH2SH, to the Sbonded type O3CrSCH2COOH, prior to the redox step. Normal acid-base equilibria of thioglycolate ( H2TGA / HTGA) and chromate species ( HCrO4 / CrO4 2) were found to be inadequate to explain the overall mechanism. Instead, the facile reactions of both O-bonded and S-bonded Cr(VI)-thioglycolate intermediates were seen to be influenced by their own proton dependency. It was found that depending on the nature of the buffer used, some catalytic effects were evident, but the complete pH profile obtained was inherently peculiar to the reaction involving the main reactants. Added metal ions such as Cu2+ and Zn2+ are implicated in the overall course of the reaction, and their effects also seem to be determined by the concentration of [H +] utilized.
巯基乙酸H2TGA含有活性巯基,可还原Cr(VI)。实验条件为[Cr(VI)]T = 0.20 mM, [TGA]T = 22 ~ 100 mM, 15.0≤T≤30.0℃,2.66≤pH≤4.66 (TGA自缓冲液)或2.74≤pH≤6.05(柠檬酸-磷酸),离子强度恒定为0.50 M (NaClO4)。采用λ = 425 nm的快速扫描停流分光光度法对反应进行了研究。反应的动力学表现出明显的光谱证据,表明中间产物的形成随后是一个较慢的双分子氧化还原过程,导致最终产物的形成。根据实验数据分析,中间体的形成涉及氧化还原步骤之前,O键的Cr(VI)-巯基乙酸酯中间体O3CrOC(O)CH2SH转化为键合型O3CrSCH2COOH。巯基乙酸酯(H2TGA / HTGA)和铬酸盐(HCrO4 / CrO4 2)的正常酸碱平衡不足以解释整个机制。相反,o键和s键Cr(VI)-巯基乙酸酯中间体的容易反应被认为受到它们自身质子依赖性的影响。研究发现,根据所用缓冲液的性质,某些催化作用是明显的,但得到的完整pH谱是涉及主要反应物的反应所特有的。添加的金属离子如Cu2+和Zn2+与整个反应过程有关,它们的作用似乎也取决于所使用的[H +]的浓度。
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引用次数: 2
The Kinetics and Mechanism of the Oxidation of Inorganic Oxysulfur Compounds by Potassium Ferrate Part IV - A Theoretical Analysis of Four Models Proposed to Explain Some of the Unusual Results for Trithionate, Tetrathionate and Pentathionate Ions 高铁酸钾氧化无机含氧硫化合物的动力学和机理——对三硫酸盐、四硫酸盐和五硫酸盐离子异常反应的四种模型的理论分析
Pub Date : 2005-01-01 DOI: 10.1515/IRM.2005.5.4.305
J. F. Read, S. Bewick
The kinetics and mechanism of the reaction between a series of inorganic oxysulfur compounds and potassium ferrate have been studied. Although a clear pattern has been developed, there are certain anomalous results, often pH dependent, which could be occurring because of hydrolysis or impurities. This paper addresses this problem by examining four theoretical models applied to some of the kinetic results obtained for trithionate, tetrathionate and pentathionate ions. The models examined are:
研究了一系列无机含氧硫化合物与高铁酸钾的反应动力学和反应机理。虽然已经形成了一个清晰的模式,但仍有某些异常结果,通常与pH值有关,这可能是由于水解或杂质而发生的。本文通过对三硫酸盐、四硫酸盐和五硫酸盐离子动力学结果的四种理论模型的研究来解决这一问题。检验的模型有:
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引用次数: 5
Kinetics and Mechanism of the Reduction of Enneamolybdonickelate(IV) by Oxalate 草酸还原enneamolydonickelate (IV)的动力学及机理
Pub Date : 2005-01-01 DOI: 10.1515/IRM.2005.5.3.167
G. Huo, Xuguang Zhao, Bao-Sheng Liu
Heteropolyacids and their salts are known as acidic and redox catalysts in some reactions [1-3]. Studies of the kinetics and mechanism of redox reactions of heteropolyacids and their salts are instructive, given their value as redox reaction catalysts. Ammonium enneamolybdonickelate(IV) {(NH4)6[NiMo9O32]6H2O} is a Waugh-type heteropolyacid salt. It can oxidize a range of substances, including organic and inorganic reagents [4]. However, very few reports on the kinetics and mechanism of this type of heteropolyacid salts as oxidant have appeared. This paper reports the kinetics and mechanism of the reduction of enneamolybdonickelate(IV) by oxalate.
杂多酸及其盐类在某些反应中被称为酸性和氧化还原催化剂[1-3]。考虑到杂多酸及其盐作为氧化还原反应催化剂的价值,研究其氧化还原反应的动力学和机理具有指导意义。膜钼酸铵(IV) {(NH4)6[NiMo9O32]6H2O}是一种沃氏型杂多酸盐。它可以氧化一系列物质,包括有机和无机试剂[4]。然而,关于这类杂多酸盐作为氧化剂的动力学和机理的报道很少。本文报道了草酸还原enneemydonickelate (IV)的动力学和机理。
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引用次数: 0
Ruthenium(III) Catalysed Oxidation of L-Alanine by Alkaline Permanganate: A Kinetic and Mechanistic Approach 钌(III)催化碱性高锰酸盐氧化l -丙氨酸的动力学和机理研究
Pub Date : 2005-01-01 DOI: 10.1515/IRM.2005.5.3.231
S. Chimatadar, A. K. Kini, S. Nandibewoor
Potassium permanganate is widely used as an oxidising agent in synthetic as well as in analytical chemistry, and also as a disinfectant. The permanganate reactions are governed by the pH of the medium. Among the six oxidation states of manganese (+2 to+ 7), permanganate, Mn(VII) is the most potent oxidation state in acid as well as in alkaline medium. The manganese chemistry involved in these multistep redox reactions provides an important source of information as the manganese intermediates are relatively easy to identify when they have sufficiently long life times. 0xidation states of the intermediates permit useful conclusions to be drawn as to the possible reaction mechanism, including the nature of intermediates. Oxidation by permanganate ion is applied extensively in organic syntheses [1-7] especially since the advent of phase transfer catalysis [3,4,6]. Kinetic studies are important Inorganic Reaction Mechanisims, Vol. 5, pp. 231-244 © 2005 Old City Publishing, Inc. Reprints available directly from the publisher Published by license under the OCP Science imprint, Photocopying permitted by license only a member of the Old City Publishing Group.
高锰酸钾在合成化学和分析化学中广泛用作氧化剂,也用作消毒剂。高锰酸盐反应受介质的pH值控制。在锰的6种氧化态(+2 ~ + 7)中,高锰酸锰(Mn(VII))在酸性和碱性介质中氧化力最强。这些多步氧化还原反应中涉及的锰化学提供了重要的信息来源,因为锰中间体在具有足够长的寿命时相对容易识别。中间体的反应状态允许对可能的反应机理得出有用的结论,包括中间体的性质。高锰酸盐离子氧化在有机合成中得到了广泛的应用[1-7],特别是相转移催化[3,4,6]的出现。动力学研究是重要的无机反应机理,Vol. 5, pp. 231-244©2005 Old City Publishing, Inc。可直接从出版商处获得重印,在OCP科学印记下通过许可出版,仅允许旧城出版集团成员的许可复印。
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引用次数: 12
The Kinetics and Mechanism of the Oxidation of Inorganic Oxysulfur Compounds by Potassium Ferrate Part III - Trithionate and Pentathionate Ions 高铁酸钾氧化无机含氧硫化合物的动力学和机理。第三部分-三硫酸盐和五硫酸盐离子
Pub Date : 2005-01-01 DOI: 10.1515/IRM.2005.5.4.281
J. F. Read, S. Bewick, Sandra C. Donaher, M. D. Eelman, J. Oakey, Catherine Schaubel, Nga Chiu Tam, Annie Thériault, K. Watson
Potassium ferrate (K2FeO4) is an effective, selective oxidizing agent, giving an environmentally benign product of Fe(II) or Fe(III). The present study completes the experimental investigation of the oxidation of the inorganic oxysulfur compounds. The kinetics and mechanism of the ferrate oxidation have been determined for the sulfite (SO23 ) [1 3], thiosulfate (S2O 3 ) [3, 4], dithionite (S2O 4 ) [3], disulfite (S2O 5 ) [3], dithionate (S2O 6 ) [5] and Inorganic Reaction Mechanisims, Vol. 5, pp. 281-304 © 2005 Old City Publishing, Inc. Reprints available directly from the publisher Published by license under the OCP Science imprint, Photocopying permitted by license only a member of the Old City Publishing Group.
高铁酸钾(K2FeO4)是一种有效的、选择性的氧化剂,可以产生对环境无害的铁(II)或铁(III)。本研究完成了无机含氧硫化合物氧化的实验研究。高铁酸盐氧化亚硫酸盐(SO23)[1 3]、硫代硫酸盐(S2O 3)[3, 4]、二硫代硫酸盐(S2O 4)[3]、二亚硫酸盐(S2O 5)[3]、二硫代酸盐(S2O 6)[5]和无机反应机理的动力学和机理研究,第五卷,281-304页©2005 Old City Publishing, Inc。可直接从出版商处获得重印,在OCP科学印记下通过许可出版,仅允许旧城出版集团成员的许可复印。
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引用次数: 5
Oxidation of Arsenous Acid by 12-Tungstocobaltate(III) Catalysed by Ruthenium(III) in Aqueous Acid Medium 酸水溶液中钌催化12-钴酸钨(III)氧化亚砷酸的研究
Pub Date : 2004-08-01 DOI: 10.1515/IRM.2004.5.2.79
B. D. Bhosale, G. Gokavi
Ruthenium(III)-catalysed arsenic(III) oxidation by 12-tungstocobaltate(III) was found to proceed with transfer of an electron from catalyst to oxidant generating an intermediate ruthenium(IV). In the next step ruthenium(IV) abstract an electron from arsenic(III) leading to form arsenic(IV), which further reacts with oxidant to give arsenic(V). The active catalyst species was RuCl5(H2O) and due to formation of the inactive higher chloro-complex, RuCl6, inhibition of the reaction occurs as chloride ion concentration increases. There was no effect of hydrogen ion concentration on the reaction due to absence of any protonation equilibria under experimental conditions. The reaction was also catalysed by alkali metal cations due to ion pair formation between 12-tungstocobaltate(III) and alkali metal cations.
钌(III)催化砷(III)被12-钨钴酸盐(III)氧化,发现电子从催化剂转移到氧化剂,生成中间钌(IV)。下一步,钌(IV)从砷(III)中提取一个电子,形成砷(IV),砷(IV)进一步与氧化剂反应生成砷(V)。活性催化剂为RuCl5(H2O),由于形成了无活性的高氯络合物RuCl6,随着氯离子浓度的增加,反应发生抑制。在实验条件下,由于没有质子化平衡,氢离子浓度对反应没有影响。由于12-钴酸钨(III)与碱金属阳离子之间形成离子对,碱金属阳离子也催化了反应。
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引用次数: 3
The Kinetics and Mechanism of the Oxidation of Phenylthioacetic Acid and Thiodiglycolic Acid by Potassium Ferrate 高铁酸钾氧化苯硫代乙酸和硫代二乙醇酸的动力学及机理
Pub Date : 2004-01-01 DOI: 10.1515/IRM.2004.5.2.135
J. F. Read, B. Griffiths, L. Lynch, K. Maccormick, Nga Chiu Tam
The kinetics and mechanism of the oxidation of phenylthioacetic acid and thiodiglycolic acid by potassium ferrate were investigated under pseudo and non pseudo first-order conditions. Phenylthioacetic acid was oxidized to the sulfone and Fe(II) within 300s and thiodiglycolic acid was oxidized to the sulfoxide and Fe(III) within 1000s. Above a pH value of 8.7 for phenylthioacetic acid and 8.3 for thiodiglycolic acid the kinetics were firstorder in the concentration of the hydrogen ions, the organosulfur compound and the ferrate ions, whereas below these pH values the kinetics were independent of the hydrogen ion concentration. A possible mechanism involves reaction between protonated ferrate and the organosulfur compound as the rate-determining step with a rate constant of 35 M-1s-1. These results are comparable with other similar compounds.
研究了高铁酸钾在准一级和非准一级条件下氧化苯硫代乙酸和硫代二乙酸的动力学和机理。苯硫乙酸在300s内被氧化为砜和铁(II),硫代二乙醇酸在1000s内被氧化为亚砜和铁(III)。当pH值为8.7时,苯硫乙酸和8.3时,氢离子浓度、有机硫化合物浓度和高铁酸盐浓度对反应动力学影响最大,而pH值低于此值时,反应动力学与氢离子浓度无关。一个可能的机制是质子化高铁酸盐和有机硫化合物之间的反应作为速率决定步骤,速率常数为35 M-1s-1。这些结果与其他类似的化合物具有可比性。
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引用次数: 3
期刊
BioInorganic Reaction Mechanisms
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