Kinetics and mechanisms of S(IV) reductions of bromite and chlorite ions

The reaction of bromite with aqueous S(IV) is first order in both reactants and is general-acid catalyzed. The reaction half-lives vary from 5 ms (p[H+] 5.9) to 210 s (p[H+] 13.1) for 0.7 mM excess S(IV) at 25 degrees C. The proposed mechanism includes a rapid reaction (k(1) = 3.0 x 10(7) M(-1) s(-1)) between BrO(2)(-) and SO(3)(2-) to form a steady-state intermediate, (O(2)BrSO(3))(3-). General acids assist the removal of an oxide ion from (O(2)BrSO(3))(3-) to form OBrSO(3)(-), which hydrolyzes rapidly to give OBr(-) and SO(4)(2-). Subsequent fast reactions between HOBr/OBr(-) and SO(3)(2-) give Br(-) and SO(4)(2-) as final products. In contrast, the chlorite reactions with S(IV) are 5-6 orders of magnitude slower. These reactions are specific-acid, not general-acid, catalyzed. In the proposed mechanism, ClO(2)(-) and SO(3)H(-)/SO(2) react to form (OClOSO(3)H)(2)(-) and (OClOSO(2))(-) intermediates which decompose to form OCl(-) and SO(4)(2-). Subsequent fast reactions between HOCl/OCl(-) and S(IV) give Cl- and SO(4)(2-) as final products. SO(2) is 6 orders of magnitude more reactive than SO(3)H-, where k(5)(SO(2)/ClO(2)(-)) = 6.26 x 10(6) M(-1) s(-1) and k(6)(SO(3)H(-)/ClO(2)(-)) = 5.5 M(-1) s(-1). Direct reaction between ClO(2)(-) and SO(3)(2-) is not observed. The presence or absence of general-acid catalysis leads to the proposal of different connectivities for the initial reactive intermediates, where a Br-S bond forms with BrO(2)(-) and SO(3)(2-), while an O-S bond forms with ClO(2)(-) and SO(3)H-.     

Ab initio chemical kinetics for reactions of ClO with Cl2O2 isomers

The mechanisms for the reactions of ClO with ClOClO, ClOOCl, and ClClO(2) have been investigated at the CCSD(T)/6-311+G(3df)//PW91PW91∕6-311+G(3df) level of theory. The rate constants for their low energy channels have been calculated by statistical theory. The results show that the main products for the reaction of ClO with ClOClO are ClOCl + ClOO, which can be produced readily by ClO abstracting the terminal O atom from ClOClO. This process occurs without an intrinsic barrier, with the predicted rate constant: k (ClO + ClOClO) = 7.26 × 10(-10) T(-0.15) × exp (-40/T) cm(3)molecule(-1)s(-1) for 200-1500 K. For the reactions of ClO + ClOOCl and ClClO(2), the lowest abstraction barriers are 7.2 and 7.3 kcal/mol, respectively, suggesting that these two reactions are kinetically unimportant in the Earth's stratosphere as their rate constants are less than 10(-14) cm(3)molecule(-1)s(-1) below 700 K. At T = 200-1500 K, the computed rate constants can be represented by k (ClO+ ClOOCl) = 1.11 × 10 (-14) T (0.87) exp (-3576/T) and k (ClO+ ClClO(2)) = 4.61 × 10(-14) T(0.53) exp (-3588/T) cm(3)molecule(-1)s(-1). For these systems, no experimental or theoretical kinetic data are available for comparison.     

S-oxygenation of thiocarbamides I: Oxidation of phenylthiourea by chlorite in acidic media

The oxidation of 1-phenyl-2-thiourea (PTU) by chlorite was studied in aqueous acidic media. The reaction is extremely complex with reaction dynamics strongly influenced by the pH of reaction medium. In excess chlorite concentrations the reaction stoichiometry involves the complete desulfurization of PTU to yield a urea residue and sulfate: 2ClO2- + PhN(H)CSNH2 + H2O --> SO4(2-) + PhN(H)CONH2 + 2Cl- + 2H+. In excess PTU, mixtures of sulfinic and sulfonic acids are formed. The reaction was followed spectrophotometrically by observing the formation of chlorine dioxide which is formed from the reaction of the reactive intermediate HOCl and chlorite: 2ClO2- + HOCl + H+ --> 2ClO2(aq) + Cl- + H2O. The complexity of the ClO2- - PTU reaction arises from the fact that the reaction of ClO2 with PTU is slow enough to allow the accumulation of ClO2 in the presence of PTU. Hence the formation of ClO2 was observed to be oligooscillatory with transient formation of ClO2 even in conditions of excess oxidant. The reaction showed complex acid dependence with acid catalysis in pH conditions higher than pKa of HClO2 and acid retardation in pH conditions of less than 2.0. The rate of oxidation of PTU was given by -d[PTU]/dt = k1[ClO2-][PTU] + k2[HClO2][PTU] with the rate law: -d[PTU]/dt = [Cl(III)](T)[PTU]0/K(a1) + [H+] [k1K(a1) + k2[H+]]; where [Cl(III)]T is the sum of chlorite and chlorous acid and K(a1) is the acid dissociation constant for chlorous acid. The following bimolecular rate constants were evaluated; k1 = 31.5+/-2.3 M(-1) s(-1) and k2 = 114+/-7 M(-1) s(-1). The direct reaction of ClO2 with PTU was autocatalytic in low acid concentrations with a stoichiometric ratio of 8:5; 8ClO2 + 5PhN(H)CSNH2 + 9H2O --> 5SO4(2-) + 5PhN(H)CONH2 + 8Cl- + 18H+. The proposed mechanism implicates HOCl as a major intermediate whose autocatalytic production determined the observed global dynamics of the reaction. A comprehensive 29-reaction scheme is evoked to describe the complex reaction dynamics.     

Kinetic origin of the chelate effect. Base hydrolysis, H-exchange reactivity, and structures of syn,anti-[Co(cyclen)(NH3)2]3+ and syn,anti-[Co(cyclen)(diamine)]3+ ions (diamine = H2N(CH2)2NH2, H2N(CH2)3NH2)

The synthesis of syn,anti-[Co(cyclen)en](ClO4)3 (1(ClO4)3) and syn,anti-[Co(cyclen)tn](ClO4)3 (2(ClO4)3) is reported, as are single-crystal X-ray structures for syn,anti-[Co(cyclen)(NH3)2](ClO4)3 (3(ClO4)3). 3(ClO4)3: orthorhombic, Pnma, a = 17.805(4) A, b = 12.123(3) A, c = 9.493(2) A, alpha = beta = gamma = 90 degrees, Z = 4, R1 = 0.030. 1(ClO4)3: monoclinic, P2(1)/n, a = 8.892(2) A, b = 15.285(3) A, c = 15.466(3) A, alpha = 90 degrees, beta = 91.05(3) degrees, gamma = 90 degrees, Z = 4, R1 = 0.0657. 2Br3: orthorhombic, Pca2(1) a = 14.170(4) A, b = 10.623(3) A, c = 12.362(4) A, alpha = beta = gamma = 90 degrees, Z = 4, R1 = 0.0289. Rate constants for H/D exchange (D2O, I = 1.0 M, NaClO4, 25 degrees C) of the syn and anti NH protons (rate law: kobs = ko + kH[OD-]) and the apical NH, and the NH3 and NH2 protons (rate law: kobs = kH[OD-]) in the 1, 2, and 3 cations are reported. Deprotonation constants (K = [Co(cyclen-H)(diamine)2+]/[Co(cyclen)(diamine)3+][OH-]) were determined for 1 (5.5 +/- 0.5 M-1) and 2 (28 +/- 3 M-1). In alkaline solution 1, 2, and 3 hydrolyze to [Co(cyclen)(OH)2]+ via [Co(cyclen)(amine)OH)]2+ monodentates. Hydrolysis of 3 is two step: kobs(1) = kOH(1)[OH-], kobs(2) = ko + kOH(2)[OH-] (kOH(1) = (2.2 +/- 0.4) x 10(4) M-1 s-1, ko = (5.1 +/- 1.2) x 10(-4) s-1, kOH(2) = 1.0 +/- 0.1 M-1 s-1). Hydrolysis of 2 is biphasic: kobs(1) = k1K[OH-]/(1 + K[OH-] (k1 = 5.0 +/- 0.2 s-1, K = 28 M-1), kobs(2) = k2K2[OH-]/(1 + K2[OH-]) (k2 = 3.5 +/- 1.2 s-1, K2 = 1.2 +/- 0.8 M-1). Hydrolysis of 1 is monophasic: kobs = k1k2KK2[OH-]2/(1 + K[OH-1])(k-1 + k2K2[OH-]) (k1 = 0.035 +/- 0.004 s-1, k-1 = 2.9 +/- 0.6 s-1, K = 5.5 M-1, k2K2 = 4.0 M-1 s-1). The much slower rate of chelate ring-opening in 1, compared to loss of NH3 from 3, is rationalized in terms of a reduced ability of the former system to allow the bond angle expansion required to produce the SN1CB trigonal bipyramidal intermediate.     

Kinetics and mechanisms of the reactions of hypochlorous acid,chlorine, and chlorine monoxide with bromite ion

The reaction between BrO2(-) and excess HOCl (p[H+] 6-7, 25.0 degrees C) proceeds through several pathways. The primary path is a multistep oxidation of HOCl by BrO(2)(-) to form ClO(3)(-) and HOBr (85% of the initial 0.15 mM BrO(2)(-)). Another pathway produces ClO(2) and HOBr (8%), and a third pathway produces BrO(3)(-) and Cl(-) (7%). With excess HOCl concentrations, Cl(2)O also is a reactive species. In the proposed mechanism, HOCl and Cl(2)O react with BrO(2)(-) to form steady-state species, HOClOBrO(-) and ClOClOBrO(-). Acid facilitates the conversion of HOClOBrO(-) and ClOClOBrO(-) to HOBrOClO(-). These reactions require a chainlike connectivity of the intermediates with alternating halogen-oxygen bonding (i.e. HOBrOClO(-)) as opposed to Y-shaped intermediates with a direct halogen-halogen bond (i.e. HOBrCl(O)O(-)). The HOBrOClO(-) species dissociates into HOBr and ClO(2)(-) or reacts with general acids to form BrOClO. The distribution of products suggests that BrOClO exists as a BrOClO.HOCl adduct in the presence of excess HOCl. The primary products, ClO(3)(-) and HOBr, are formed from the hydrolysis of BrOClO.HOCl. A minor hydrolysis path for BrOClO.HOCl gives BrO(3)(-) and Cl(-). An induction period in the formation of ClO(2) is observed due to the buildup of ClO(2)(-), which reacts with BrOClO.HOCl to give 2 ClO(2) and Br(-). Second-order rate constants for the reactions of HOCl and Cl(2)O with BrO(2)(-) are k(1)(HOCl) = 1.6 x 10(2) M(-1) s(-1) and k(1)(Cl)()2(O) = 1.8 x 10(5) M(-)(1) s(-)(1). When Cl(-) is added in large excess, a Cl(2) pathway exists in competition with the HOCl and Cl(2)O pathways for the loss of BrO(2)(-). The proposed Cl(2) pathway proceeds by Cl(+) transfer to form a steady-state ClOBrO species with a rate constant of k(1)(Cl2) = 8.7 x 10(5) M(-1) s(-1).     

Oxyhalogen-sulfur chemistry: kinetics and mechanism of oxidation of N-acetylthiourea by chlorite and chlorine dioxide

The oxidation reactions of N-acetylthiourea (ACTU) by chlorite and chlorine dioxide were studied in slightly acidic media. The ACTU-ClO(2)(-) reaction has a complex dependence on acid with acid catalysis in pH > 2 followed by acid retardation in higher acid conditions. In excess chlorite conditions the reaction is characterized by a very short induction period followed by a sudden and rapid formation of chlorine dioxide and sulfate. In some ratios of oxidant to reductant mixtures, oligo-oscillatory formation of chlorine dioxide is observed. The stoichiometry of the reaction is 2:1, with a complete desulfurization of the ACTU thiocarbamide to produce the corresponding urea product: 2ClO(2)(-) + CH(3)CONH(NH(2))C=S + H(2)O --> CH(3)CONH(NH(2))C=O + SO(4)(2-) + 2Cl(-) + 2H(+) (A). The reaction of chlorine dioxide and ACTU is extremely rapid and autocatalytic. The stoichiometry of this reaction is 8ClO(2)(aq) + 5CH(3)CONH(NH(2))C=S + 9H(2)O --> 5CH(3)CONH(NH(2))C=O + 5SO(4)(2-) + 8Cl(-) + 18H(+) (B). The ACTU-ClO(2)(-) reaction shows a much stronger HOCl autocatalysis than that which has been observed with other oxychlorine-thiocarbamide reactions. The reaction of chlorine dioxide with ACTU involves the initial formation of an adduct which hydrolyses to eliminate an unstable oxychlorine intermediate HClO(2)(-) which then combines with another ClO(2) molecule to produce and accumulate ClO(2)(-). The oxidation of ACTU involves the successive oxidation of the sulfur center through the sulfenic and sulfinic acids. Oxidation of the sulfinic acid by chlorine dioxide proceeds directly to sulfate bypassing the sulfonic acid. Sulfonic acids are inert to further oxidation and are only oxidized to sulfate via an initial hydrolysis reaction to yield bisulfite, which is then rapidly oxidized. Chlorine dioxide production after the induction period is due to the reaction of the intermediate HOCl species with ClO(2)(-). Oligo-oscillatory behavior arises from the fact that reactions that form ClO(2) are comparable in magnitude to those that consume ClO(2), and hence the assertion of each set of reactions is based on availability of reagents that fuel them. A computer simulation study involving 30 elementary and composite reactions gave a good fit to the induction period observed in the formation of chlorine dioxide and in the autocatalytic consumption of ACTU in its oxidation by ClO(2).     

Kinetics and mechanisms of chlorine dioxide oxidation of tryptophan

The reactions of aqueous ClO2 (*) and tryptophan (Trp) are investigated by stopped-flow kinetics, and the products are identified by high-performance liquid chromatography (HPLC) coupled with electrospray ionization mass spectrometry and by ion chromatography. The rates of ClO2 (*) loss increase from pH 3 to 5, are essentially constant from pH 5 to 7, and increase from pH 7 to 10. The reactions are first-order in Trp with variable order in ClO2 (*). Below pH 5.0, the reactions are second- or mixed-order in [ClO2 (*)], depending on the chlorite concentration. Above pH 5.0, the reactions are first-order in [ClO2 (*)] in the absence of added chlorite. At pH 7.0, the Trp reaction with ClO2 (*) is first-order in each reactant with a second-order rate constant of 3.4 x 10(4) M(-1) s(-1) at 25.0 degrees C. In the proposed mechanism, the initial reaction is a one-electron oxidation to form a tryptophyl radical cation and chlorite ion. The radical cation deprotonates to form a neutral tryptophyl radical that combines rapidly with a second ClO 2 (*) to give an observable, short-lived adduct ( k obs = 48 s(-1)) with proposed C(H)-OClO bonding. This adduct decays to give HOCl in a three-electron oxidation. The overall reaction consumes two ClO2 (*) per Trp and forms ClO2- and HOCl. This corresponds to a four-electron oxidation. Decay of the tryptophyl-OClO adduct at pH 6.4 gives five initial products that are observed after 2 min and are separated by HPLC with elution times that vary from 4 to 17 min (with an eluent of 6.3% CH 3OH and 0.1% CH 3COOH). Each of these products is characterized by mass spectrometry and UV-vis spectroscopy. One initial product with a molecular weight of 236 decays within 47 min to yield the most stable product, N-formylkynurenine (NFK), which also has a molecular weight of 236. Other products also are observed and examined.     

Ab initio study of the ClO + NH2 reaction: prediction of the total rate constant and product branching ratios

The mechanism for ClO + NH2 has been investigated by ab initio molecular orbital and transition-state theory calculations. The species involved have been optimized at the B3LYP/6-311+G(3df,2p) level and their energies have been refined by single-point calculations with the modified Gaussian-2 method, G2M(CC2). Ten stable isomers have been located and a detailed potential energy diagram is provided. The rate constants and branching ratios for the low-lying energy channel products including HCl + HNO, Cl + NH2O, and HOCl + 3NH (X(3)Sigma(-)) are calculated. The result shows that formation of HCl + HNO is dominant below 1000 K; over 1000 K, Cl + NH2O products become dominant. However, the formation of HOCl + 3NH (X(3)Sigma(-)) is unimportant below 1500 K. The pressure-independent individual and total rate constants can be expressed as k1(HCl + HNO) = 4.7 x 10(-8)(T(-1.08)) exp(-129/T), k(2)(Cl + NH2O) = 1.7 x 10(-9)(T(-0.62)) exp(-24/T), k3(HOCl + NH) = 4.8 x 10(-29)(T5.11) exp(-1035/T), and k(total) = 5.0 x 10(-9)(T(-0.67)) exp(-1.2/T), respectively, with units of cm(3) molecule(-1) s(-1), in the temperature range of 200-2500 K.     

OClO与OH反应机理的理论研究

用密度泛函B3LYP/-311+G~(* *)和级电子相关倒映 合簇CCSD(T)/6-311+G~(* *)方法研究了OClO与OH反应的微观机理，研究结果表明：该反应经过缔合、H转移 和离解等复杂过程，最终得到四种产物，分别为HOCl+O_2，HCl+O_3,ClO+HO_2和 HOClO_2,从能量上看，形成HOCl+O_2和HCl+O_3的通道更容易进行，而形成 ClO+HO_2的通首在动力学上是最不利的。     

Ab initio/density functional theory and multichannel RRKM study for the ClO + CH2O reaction

The potential energy surface for the CH(2)O + ClO reaction was calculated at the QCISD(T)/6-311G(2d,2p)//B3LYP/6-311G(d,p) level of theory. The rate constants for the lower barrier reaction channels producing HOCl + HCO, H atom, OCH(2)OCl, cis-HC(O)OCl and trans-HC(O)OCl have been calculated by TST and multichannel RRKM theory. Over the temperature range of 200-2000 K, the overall rate constants were k(200-2000K) = 1.19 x 10(-13)T(0.79) exp(-3000.00/T). At 250 K, the calculated overall rate constant was 5.80 x 10(-17) cm(3) molecule(-1) s(-1), which was in good agreement with the experimental upper limit data. The calculated results demonstrated that the formation of HOCl + HCO was the dominant reaction channel and was exothermic by 9.7 kcal/mol with a barrier of 5.0 kcal/mol. When it retrograded to the reactants CH(2)O + ClO, an energy barrier of 14.7 kcal/mol is required. Furthermore, when HOCl decomposed into H + ClO, the energy required was 93.3 kcal/mol. These results suggest that the decomposition in both the forward and backward directions for HOCl would be difficult in the ground electronic state.     

Chlorine dioxide reduction by aqueous iron(II) through outer-sphere and inner-sphere electron-transfer pathways

The reduction of ClO(2) to ClO(2)(-) by aqueous iron(II) in 0.5 M HClO(4) proceeds by both outer-sphere (86%) and inner-sphere (14%) electron-transfer pathways. The second-order rate constant for the outer-sphere reaction is 1.3 x 10(6) M(-1) s(-1). The inner-sphere electron-transfer reaction takes place via the formation of FeClO(2)(2+) that is observed as an intermediate. The rate constant for the inner-sphere path (2.0 x 10(5) M(-1) s(-1)) is controlled by ClO(2) substitution of a coordinated water to give an inner-sphere complex between ClO(2) and Fe(II) that very rapidly transfers an electron to give (Fe(III)(ClO(2)(-))(H(2)O)(5)(2+))(IS). The composite activation parameters for the ClO(2)/Fe(aq)(2+) reaction (inner-sphere + outer-sphere) are the following: DeltaH(r)++ = 40 kJ mol(-1); DeltaS(r)++ = 1.7 J mol(-1) K(-1). The Fe(III)ClO(2)(2+) inner-sphere complex dissociates to give Fe(aq)(3+) and ClO(2)(-) (39.3 s(-1)). The activation parameters for the dissociation of this complex are the following: DeltaH(d)++= 76 kJ mol(-1); DeltaS(d)++= 32 J K(-1) mol(-1). The reaction of Fe(aq)(2+) with ClO(2)(-) is first order in each species with a second-order rate constant of k(ClO2)- = 2.0 x 10(3) M(-1) s(-1) that is five times larger than the rate constant for the Fe(aq)(2+) reaction with HClO(2) in H(2)SO(4) medium ([H(+)] = 0.01-0.13 M). The composite activation parameters for the Fe(aq)(2+)/Cl(III) reaction in H(2)SO(4) are DeltaH(Cl(III))++ = 41 kJ mol(-1) and DeltaS(Cl(III))++ = 48 J mol(-1) K(-1).     

Kinetics of the OH + ClOOCl and OH + Cl2O reactions: experiment and theory

The rate coefficients for the reactions OH + ClOOCl --> HOCl + ClOO (eq 5) and OH + Cl2O --> HOCl + ClO (eq 6) were measured using a fast flow reactor coupled with molecular beam quadrupole mass spectrometry. OH was detected using resonance fluorescence at 309 nm. The measured Arrhenius expressions for these reactions are k5 = (6.0 +/- 3.5) x 10(-13) exp((670 +/- 230)/T) cm(3) molecule(-1) s(-1) and k6 = (5.1 +/- 1.5) x 10(-12) exp((100 +/- 92)/T) cm(3) molecule(-1) s(-1), respectively, where the uncertainties are reported at the 2sigma level. Investigation of the OH + ClOOCl potential energy surface using high level ab initio calculations indicates that the reaction occurs via a chlorine abstraction from ClOOCl by the OH radical. The lowest energy pathway is calculated to proceed through a weak ClOOCl-OH prereactive complex that is bound by 2.6 kcal mol(-1) and leads to ClOO and HOCl products. The transition state to product formation is calculated to be 0.59 kcal mol(-1) above the reactant energy level. Inclusion of the OH + ClOOCl rate data into an atmospheric model indicates that this reaction contributes more than 15% to ClOOCl loss during twilight conditions in the Arctic stratosphere. Reducing the rate of ClOOCl photolysis, as indicated by a recent re-examination of the ClOOCl UV absorption spectrum, increases the contribution of the OH + ClOOCl reaction to polar stratospheric loss of ClOOCl.     

Oxidation of chlorine(III) by hypobromous acid: kinetics and mechanism

The kinetics and mechanism of the chlorine(III)-HOBr reaction were studied by the stopped-flow method under acidic conditions, pH 1.0-3.0, in 1.0 M NaClO(4) and at 25.0 degrees C. The overall redox process occurs in two consecutive steps via the formation of the BrClO(2) intermediate. The electron transfer reactions are coupled with bromine hydrolysis, the formation of the tribromide ion, and the protolytic equilibrium of chlorine(III). On the basis of simultaneous evaluation of the kinetic traces, the following rate constants were obtained for the redox steps: HClO(2) + HOBr right harpoon over left harpoon BrClO(2) + H(2)O, k(3) = (3.34 +/- 0.02) x 10(4) M(-1) s(-1), k(-3) = (3.5 +/- 1.3) x 10(3) s(-1); BrClO(2) + ClO(2)(-)<==>2ClO(2) + Br(-), k(4) = (2.9 +/- 1.0) x 10(7) M(-1) s(-1). The second step was practically irreversible under the conditions applied, and the value of k(-4) could not be determined. The equilibrium constant for the formation of BrClO(2), K(3) = 9.5 M(-1), was calculated from the kinetic results, and it was confirmed that this species is a very powerful oxidant. The redox potential was also estimated for the BrClO(2) + e(-) = Br(-) + ClO(2) reaction: epsilon(0) approximately 1.70 V.     

Copper(I) and copper(II) complexes possessing cross-linked imidazole-phenol ligands: structures and dioxygen reactivity

Catalytic reduction of O2 to H2O, and coupling to membrane proton translocation, occurs at the heterobinuclear heme a3-CuB active site of cytochrome c oxidase. One of the CuB ligated histidines is cross-linked to a neighboring tyrosine (C-N bond; tyrosine C6 and histidine epsilon-nitrogen), and the protic residue of this cross-linked His-Tyr moiety is proposed to participate as both an electron and a proton donor in the catalytic dioxygen reduction event. To provide insight into the chemistry of such a moiety, we have synthesized and characterized tetra- and tridentate pyridylalkylamine chelate ligands {LN4OR and LN3OR (R = H or Me)}, which include an imidazole-phenol (or anisole) cross-link and their copper(I/II) complexes. [CuI(LN4OH)]B(C6F5)4 (1) reacts with dioxygen at -80 degrees C in THF, forming an unstable trans-mu-1,2-peroxodicopper(II)complex, which subsequently converts to a dimeric copper(II)-phenolate complex [{Cu(LN4O-)}2](B(C6F5)4)2 (5a). The close analogue [CuI(LN4OMe)]B(C6F5)4 (3) binds dioxygen reversibly at -80 degrees C in tetrahydrofuran. Stopped-flow kinetics of the reaction [CuI(LN3OH)]ClO4 (2) with O2 in CH2Cl2 indicate a steady formation of the purple dimeric product [{Cu(LN3O-)}2](ClO4)2 (5b), which has been analyzed in the temperature range from -40 to +20 degrees C, DeltaH = -9.6 (6) kJ mol-1, DeltaS = -168 (2) J mol-1 K-1 (k(-40 degrees C) = 1.05(4) x 106 and k(+20 degrees C) = 4.6(2) x 105 M-2 s-1). The X-ray crystal structures of 1, [CuII(LN3OH)(MeOH)(OClO3-)](ClO4) (4), 5a, and 5b are reported.     

Hypohalite ion catalysis of the disproportionation of chlorine dioxide

The disproportionation of chlorine dioxide in basic solution to give ClO2- and ClO3- is catalyzed by OBr- and OCl-. The reactions have a first-order dependence in both [ClO2] and [OX-] (X = Br, Cl) when the ClO2- concentrations are low. However, the reactions become second-order in [ClO2] with the addition of excess ClO2-, and the observed rates become inversely proportional to [ClO2-]. In the proposed mechanisms, electron transfer from OX- to ClO2(k1OBr- = 2.05 +/- 0.03 M(-1) x s(-1) for OBr(-)/ClO2 and k1OCl-= 0.91 +/- 0.04 M(-1) x s(-1) for OCl-/ClO2) occurs in the first step to give OX and ClO2-. This reversible step (k1OBr-/k(-1)OBr = 1.3 x 10(-7) for OBr-/ClO2, / = 5.1 x 10(-10) for OCl-/ClO2) accounts for the observed suppression by ClO2-. The second step is the reaction between two free radicals (XO and ClO2) to form XOClO2. These rate constants are = 1.0 x 10(8) M(-1) x s(-1) for OBr/ClO2 and = 7 x 10(9) M(-1) x s(-1) for OCl/ClO2. The XOClO2 adduct hydrolyzes rapidly in the basic solution to give ClO3- and to regenerate OX-. The activation parameters for the first step are DeltaH1(++) = 55 +/- 1 kJ x mol(-1), DeltaS1(++) = - 49 +/- 2 J x mol(-1) x K(-1) for the OBr-/ClO2 reaction and DeltaH1(++) = 61 +/- 3 kJ x mol(-1), DeltaS1(++) = - 43 +/- 2 J x mol(-1) x K(-1) for the OCl-/ClO2 reaction.     

Kinetics and mechanism of catalytic decomposition and oxidation of chlorine dioxide by the hypochlorite ion

The oxidation of ClO(2) by OCl(-)is first order with respect to both reactants in the neutral to alkaline pH range: -d[ClO(2)]/dt = 2k(OCl)[ClO(2)][OCl(-)]. The rate constant (T = 298 K, mu = 1.0 M NaClO(4)) and activation parameters are k(OCl) = 0.91 +/- 0.02 M(-1) s(-1), DeltaH = 66.5 +/- 0.9 kJ/mol, and DeltaS(++) = -22.3 +/- 2.9 J/(mol K). In alkaline solution, pH > 9, the primary products of the reaction are the chlorite and chlorate ions and consumption of the hypochlorite ion is not observed. The hypochlorite ion is consumed in increasing amounts, and the production of the chlorite ion ceases when the pH is decreased. The stoichiometry is kinetically controlled, and the reactants/products ratios are determined by the relative rates of the production and consumption of the chlorite ion in the ClO(2)/OCl(-) and HOCl/ClO(2)(-) reactions, respectively.     

Short-lived quinonoid species from 5,6-dihydroxyindole dimers en route to eumelanin polymers: integrated chemical, pulse radiolytic, and quantum mechanical investigation

The transient species formed by oxidation of three dimers of 5,6-dihydroxyindole (1), a major building block of the natural biopolymer eumelanin, have been investigated. Pulse radiolytic oxidation of 5,5',6,6'-tetrahydroxy-2,4'-biindolyl (3) and 5,5',6,6'-tetrahydroxy-2,7'-biindolyl (4) led to semiquinones absorbing around 450 nm, which decayed with second-order kinetics (2k=2.8x10(9) and 1.4x10(9) M-1 s-1, respectively) to give the corresponding quinones (500-550 nm). 5,5',6, 6'-Tetrahydroxy-2,2'-biindolyl (2), on the other hand, furnished a semiquinone (lamdamax=480 nm) which disproportionated at a comparable rate (2k=3x10(9) M-1 s-1) to give a relatively stable quinone (lamdamax=570 nm). A quantum mechanical investigation of o-quinone, quinonimine, and quinone methide structures of 2-4 suggested that oxidized 2-4 exist mainly as 2-substituted extended quinone methide tautomers. Finally, an oxidation product of 3 was isolated for the first time and was formulated as the hydroxylated derivative 5 arising conceivably by the addition of water to the quinone methide intermediate predicted by theoretical analysis. Overall, these results suggest that the oxidation chemistry of biindolyls 2-4 differs significantly from that of the parent 1, whereby caution must be exercised before concepts that apply strictly to the mode of coupling of 1 are extended to higher oligomers.     

Reactive sulfur species: kinetics and mechanism of the equilibrium between cysteine sulfenyl thiocyanate and cysteine thiosulfinate ester in acidic aqueous solution

The kinetics and mechanism of the hydrolysis of cysteine sulfenyl thiocyanate (CySSCN) to give cysteine thiosulfinate ester (CyS(=O)SCy) have been investigated between pH 0 and 4. The reaction is reversible. The hydrolysis of CySSCN is second-order in [CySSCN] and inverse first-order in [H+] and [SCN-]. The following mechanism is proposed for the hydrolysis of CySSCN (where the charge depends upon the pH): CySSCN0/+ + H2O <==>CySOH0/+ + SCN- + H+, CySOH0/+ + CySSCN0/+ --> CyS(=O)SCy0/+/2+ + SCN- + H+; k1 = 3.36 +/- 0.01 x 10-3 s-1, K1k2 = 0.13 +/- 0.05 Ms-1 (which yields k2/k-1 = 39 M). The observed rate law rules out alternative mechanisms for 1 0.4 M). The following mechanism is proposed: CyS(=O)SCy2+ + H+ <==> CyS(OH)=SCy3+, Ka; CyS(OH)SCy3+ + SCN- --> CySOH+ + CySSCN+, k-2 = 0.239 +/- 0.007 M-2s-1/Ka M-1. Since cysteine sulfenic acids are known to play an important function in many enzymes, and SCN- exists in abundance in physiologic fluids, we discuss the possible role of sulfenyl thiocyanates in vivo.     

Ab initio chemical kinetic study on the reactions of ClO with C2H2 and C2H4

The mechanisms for the reactions of ClO with C(2)H(2) and C(2)H(4) have been investigated at the CCSD(T)/CBS level of theory. The results show that in both systems, the interaction between the Cl atom of the ClO radical and the triple and double bonds of C(2)H(2) and C(2)H(4) forms prereaction van der Waals complexes with the O-Cl bond pointing perpendicularly toward the π-bonds, both with 2.1 kcal/mol binding energies. The mechanism is similar to those of the HO-C(2)H(2)/C(2)H(4) systems. The rate constants for the low energy channels have been predicted by statistical theory. For the reaction of ClO and C(2)H(2), the main channels are the production of CH(2)CO + Cl (k(1a)) and CHCO + HCl (k(1b)), with k(1a) = 1.19 × 10(-15)T(1.18) exp(-5814/T) and k(1b) = 6.94 × 10(-21) × T(2.60) exp(-6587/T) cm(3) molecule(-1) s(-1). For the ClO + C(2)H(4) reaction, the main pathway leads to C(2)H(4)O + Cl (k(2a)) with the predicted rate constant k(2a) = 2.13 × 10(-17)T(1.52) exp(-3849/T) in the temperature range of 300-3000 K. These rate constants are pressure-independent below 100 atm.     

Synthesis of acetimino complexes of Pt(II) and Pt(IV) and the first heteronuclear mu-acetimido complexes

The reactions of [Ag(NH=CMe2)2]ClO4 with cis-[PtCl2L2] in a 1:1 molar ratio give cis-[PtCl(NH=CMe2)(PPh3)2]ClO4 (1cis) or cis-[PtCl(NH=CMe2)2(dmso)]ClO4 (2), and in 2:1 molar ratio, they produce [Pt(NH=CMe2)2L2](ClO4)2 [L = PPh3 (3), L2= tbbpy = 4,4'-di-tert-butyl-2,2'-dipyridyl (4)]. Complex 2 reacts with PPh3 (1:2) to give trans-[PtCl(NH=CMe2)(PPh3)2]ClO(4) (1trans). The two-step reaction of cis-[PtCl2(dmso)2], [Au(NH=CMe2)(PPh3)]ClO4, and PPh3 (1:1:1) gives [SP-4-3]-[PtCl(NH=CMe2)(dmso)(PPh3)]ClO4 (5). The reactions of complexes 2 and 4 with PhICl2 give the Pt(IV) derivatives [OC-6-13]-[PtCl3(NH=CMe2)(2)(dmso)]ClO4 (6) and [OC-6-13]-[PtCl2(NH=CMe2)2(dtbbpy)](ClO4)2 (7), respectively. Complexes 1cis and 1trans react with NaH and [AuCl(PPh3)] (1:10:1.2) to give cis- and trans-[PtCl{mu-N(AuPPh3)=CMe2}(PPh3)2]ClO4 (8cis and 8trans), respectively. The crystal structures of 4.0.5Et2O.0.5Me2CO and 6 have been determined; both exhibit pseudosymmetry.