Quantum Chemical Study on the Reaction Mechanism of OBrO Radical with OH Radical

The reaction mechanism of OBrO with OH has been studied using the B3LYP/6-311 G(d,p) and the high-level electron-correlation CCSD(T)/6-311 G(d,p) at single-point. The results show that the title reaction could probably proceed by four possible schemes, generating HOBr O2, HBr O3, BrO HO2 and HOBrO2 products, respectively. The main channel is the one to yield HOBr O2. The whole reaction involves the formation of three-membered, four-membered and five-membered rings, followed by the complicated processes of association,H-shift, Br-shift and dissociation. All routes are exothermic.     

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).     

Kinetics and mechanisms of bromine chloride reactions with bromite and chlorite ions

Chloride ion catalyzes the reactions of HOBr with bromite and chlorite ions in phosphate buffer (p[H(+)] 5 to 7). Bromine chloride is generated in situ in small equilibrium concentrations by the addition of excess Cl(-) to HOBr. In the BrCl/ClO(2)(-) reaction, where ClO(2)(-) is in excess, a first-order rate of formation of ClO(2) is observed that depends on the HOBr concentration. The rate dependencies on ClO(2)(-), Cl(-), H(+), and buffer concentrations are determined. In the BrCl/BrO(2)(-) reaction where BrCl is in pre-equilibrium with the excess species, HOBr, the loss of absorbance due to BrO(2)(-) is followed. The dependencies on Cl(-), HOBr, H(+), and HPO(4)(2)(-) concentrations are determined for the BrCl/BrO(2)(-) reaction. In the proposed mechanisms, the BrCl/ClO(2)(-) and BrCl/BrO(2)(-) reactions proceed by Br(+) transfer to form steady-state levels of BrOClO and BrOBrO, respectively. The rate constant for the BrCl/ClO(2)(-) reaction [k(Cl)(2)]is 5.2 x 10(6) M(-1) s(-1) and for the BrCl/BrO(2)(-) reaction [k(Br)(2)]is 1.9 x 10(5) M(-1) s(-1). In the BrCl/ClO(2)(-) case, BrOClO reacts with ClO(2)(-) to form two ClO(2) radicals and Br(-). However, the hydrolysis of BrOBrO in the BrCl/BrO(2)(-) reaction leads to the formation of BrO(3)(-) and Br(-).     

Reduction and oxidation of hydroperoxo rhodium(III) complexes by halides and hypobromous acid

Oxygen atom transfer from trans-L(H(2)O)RhOOH(2+) [L = [14]aneN(4) (L(1)), meso-Me(6)[14]aneN(4) (L(2)), and (NH(3))(4)] to iodide takes place according to the rate law -d[L(H(2)O)RhOOH(2+)]/dt = k(I)[L(H(2)O)RhOOH(2+)][I(-)][H(+)]. At 0.10 M ionic strength and 25 degrees C, the rate constant k(I)/M(-)(2) s(-)(1) has values of 8.8 x 10(3) [L = (NH(3))(4)], 536 (L(1)), and 530 (L(2)). The final products are LRh(H(2)O)(2)(3+) and I(2)/I(3)(-). The (NH(3))(4)(H(2)O)RhOOH(2+)/Br(-) reaction also exhibits mixed third-order kinetics with k(Br) approximately 1.8 M(-)(2) s(-)(1) at high concentrations of acid (close to 1 M) and bromide (close to 0.1 M) and an ionic strength of 1.0 M. Under these conditions, Br(2)/Br(3)(-) is produced in stoichiometric amounts. As the concentrations of acid and bromide decrease, the reaction begins to generate O(2) at the expense of Br(2), until the limit at which [H(+)] 2(NH(3))(4)(H(2)O)RhOH(2+) + O(2); i.e., the reaction has turned into the bromide-catalyzed disproportionation of coordinated hydroperoxide. In the proposed mechanism, the hydrolysis of the initially formed Br(2) produces HOBr, the active oxidant for the second equivalent of (NH(3))(4)(H(2)O)RhOOH(2+). The rate constant k(HOBr) for the HOBr/(NH(3))(4)(H(2)O)RhOOH(2+) reaction is 2.9 x 10(8) M(-)(1) s(-)(1).     

Uncatalyzed reactions in the classical Belousov-Zhabotinsky system. 2. The malonic acid-bromate reaction in acidic media

The title reaction was studied with various techniques in 1 M sulfuric acid, a usual medium for the oscillatory Belousov-Zhabotinsky (BZ) reaction. It was found to be a more complex process than the bromomalonic acid (BrMA)-BrO3- reaction studied previously in the first part of this work. Malonic acid (MA) can react with acidic bromate by two parallel mechanisms. The main aim of the present research was to determine the mechanisms, the rate laws, and the rate constants for these parallel channels. In one reaction channel the first molecular products are glyoxalic acid (GOA) and CO2 while in the other channel mesoxalic acid (MOA) is the first molecular intermediate, that is, no CO2 is formed in this step. To prove these two independent routes specific colorimetric techniques were developed to determine GOA and MOA selectively. The rate of the GOA channel was determined by following the rate of the carbon dioxide evolution characteristic for this reaction route. In this step, regarding it as an overall process, one MA is oxidized to GOA and CO2 and one BrO3- is reduced to HOBr, which forms BrMA with another MA. The initial rate of the GOA channel is a bilinear function of the initial MA and BrO3- concentrations with a second-order rate constant k(GOA)= 2.4 x 10(-7) M(-1) s(-1). The rate of the other channel was calculated from the rate of the BrO3- consumption measured in separate experiments, assuming that the measured depletion is a sum of two separate terms reflecting the consumptions due to the two independent channels. In the MOA channel one MA is oxidized to MOA and one BrO3- is consumed while another MA is brominated as in the GOA channel. It was found that the initial rate of the MOA channel is also a bilinear function of the MA and BrO3- concentrations with a second-order rate constant k(MOA)= 2.46 x 10(-6) M(-1) s(-1). Separate chemical mechanisms are suggested for both channels. In all of the various bromate-substrate reactions of these mechanisms oxygen atom transfer from the bromate to the substrate occurs generating bromous acid intermediate. This can be of high importance in BZ systems as bromous acid is the autocatalytic intermediate there. GOA and MOA also can be oxidized by acidic bromate but a study of these reactions will be published later.     

Kinetics and mechanisms of the ozone/bromite and ozone/chlorite reactions

Ozone reactions with XO(2)(-) (X = Cl or Br) are studied by stopped-flow spectroscopy under pseudo-first-order conditions with excess XO(2)(-). The O(3)/XO(2)(-) reactions are first-order in [O(3)] and [XO(2)(-)], with rate constants k(1)(Cl) = 8.2(4) x 10(6) M(-1) s(-1) and k(1)(Br) = 8.9(3) x 10(4) M(-1) s(-1) at 25.0 degrees C and mu = 1.0 M. The proposed rate-determining step is an electron transfer from XO(2)(-) to O(3) to form XO(2) and O(3)(-). Subsequent rapid reactions of O(3)(-) with general acids produce O(2) and OH. The OH radical reacts rapidly with XO(2)(-) to form a second XO(2) and OH(-). In the O(3)/ClO(2)(-) reaction, ClO(2) and ClO(3)(-) are the final products due to competition between the OH/ClO(2)(-) reaction to form ClO(2) and the OH/ClO(2) reaction to form ClO(3)(-). Unlike ClO(2), BrO(2) is not a stable product due to its rapid disproportionation to form BrO(2)(-) and BrO(3)(-). However, kinetic spectra show that small but observable concentrations of BrO(2) form within the dead time of the stopped-flow instrument. Bromine dioxide is a transitory intermediate, and its observed rate of decay is equal to half the rate of the O(3)/BrO(2)(-) reaction. Ion chromatographic analysis shows that O(3) and BrO(2)(-) react in a 1/1 ratio to form BrO(3)(-) as the final product. Variation of k(1)(X) values with temperature gives Delta H(++)(Cl) = 29(2) kJ mol(-1), DeltaS(++)(Cl) = -14.6(7) J mol(-1) K(-1), Delta H(++)(Br) = 54.9(8) kJ mol(-1), and Delta S(++)(Br) = 34(3) J mol(-1) K(-1). The positive Delta S(++)(Br) value is attributed to the loss of coordinated H(2)O from BrO(2)(-) upon formation of an [O(3)BrO(2)(-)](++) activated complex.     

Activation energy for the disproportionation of HBrO2 and estimated heats of formation of HBrO2 and BrO2

The kinetics of the reaction HBrO(2) + HBrO(2) --> HOBr + BrO(3)(-) + H(+) is investigated in aqueous HClO(4) (0.04-0.9 M) and H(2)SO(4) (0.3-0.9 M) media and at temperatures in the range 15-38 degrees C. The reaction is found to be cleanly second order in [HBrO(2)], with the experimental rate constant having the form k(exp) = k + k'[H(+)]. The half-life of the reaction is on the order of a few tenths of a second in the range 0.01 M < [HBrO(2)](0) < 0.02 M. The detailed mechanism of this reaction is discussed. The activation parameters for kare found to be E(double dagger) = 19.0 +/- 0.9 kJ/mol and DeltaS(double dagger) = -132 +/- 3 J/(K mol) in HClO(4), and E(double dagger) = 23.0 +/- 0.5 kJ/mol and DeltaS(double dagger) = -119 +/- 1 J/(K mol) in H(2)SO(4). The activation parameters for k' are found to be E(double dagger) = 25.8 +/- 0.5 kJ/mol and DeltaS(double dagger) = -106 +/- 1 J/(K mol) in HClO(4), and E(double dagger) = 18 +/- 3 kJ/mol and DeltaS(double dagger) = -130 +/- 11 J/(K mol) in H(2)SO(4). The values Delta(f)H(29)(8)(0)[BrO(2)(aq)] = 157 kJ/mol and Delta(f)H(29)(8)(0)[HBrO(2)(aq)] = -33 kJ/mol are estimated using a trend analysis (bond strengths) based on the assumption Delta(f)H(29)(8)(0)[HBrO(2)(aq)] lies between Delta(f)H(29)(8)(0)[HOBr(aq)] and Delta(f)H(29)(8)(0)[HBrO(3)(aq)] as Delta(f)H(29)(8)(0)[HClO(2)(aq)] lies between Delta(f)H(29)(8)(0)[HOCl(aq)] and Delta(f)H(29)(8)(0)[HClO(3)(aq)]. The estimated value of Delta(f)H(29)(8)(0)[BrO(2)(aq)] agrees well with calculated gas-phase values, but the estimated value of Delta(f)H(29)(8)(0)[HBrO(2)(aq)], as well as the tabulated value of Delta(f)H(29)(8)(0)[HClO(2)(aq)], is in substantial disagreement with calculated gas-phase values. Values of Delta(r)H(0) are estimated for various reactions involving BrO(2) or HBrO(2).     

BrO-H2O 及 HOBr-H2O复合物偶合方式的理论研究

在6-311++G(d,p)水平上采用四种方法讨论了两种BrO-H₂O和三种HOBr-H₂O复合物的构型性质。在两种BrO-H₂O复合物中，结合能为11.37–13.92 J/mol的复合物2 （电子态为²A′）最稳定，该复合物是通过BrO中的Br原子和水中的O原子结合的。三种HOBr-H₂O复合物中，复合物3和4的结合能约为16.30–21.32 J/mol，三种复合物的稳定顺序为：复合物3 ≈ 复合物4 > 复合物5。     

Uncatalyzed reactions in the classical Belousov-Zhabotinsky system. I. Reactions of bromomalonic acid with acidic bromate and with HOBr

The uncatalyzed reactions of bromomalonic acid (BrMA) with acidic bromate and with hypobromous acid were studied in 1 M sulfuric acid, a usual medium for the oscillatory Belousov-Zhabotinsky (BZ) reaction, by following the rate of the carbon dioxide evolution associated with these reactions. In addition, the decarboxylation rate of dibromomalonic acid (Br2MA) was also measured to determine the first-order rate constant of its decomposition (4.65 x 10(-5) s(-1) in 1 M H2SO4). The dependence of that rate constant on the hydrogen ion concentration suggests a carbocation formation. A slow oligomerization of BrMA observed in sulfuric acid solutions is also rationalized as a carbocationic process. The initial rate of the BrMA-BrO3- reaction is a bilinear function of the BrMA and BrO3- concentrations with a second-order rate constant of 3.8 x 10(-4) M(-1) s(-1). When a great excess of BrO3- is applied, then BrMA is oxidized mostly to CO2. A reaction scheme compatible with the experimental finding is also given. On the other hand, when less BrO3- and more organic substrate - BrMA or malonic acid (MA)--is applied, then addition reactions of various carbocations with the enol form of the organic substrates should be taken into account in later stages of the reaction. It was discovered that HOBr, which brominates BrMA to Br2MA when BrMA is in excess, can also oxidize BrMA when HOBr is in excess. As Br2MA does not react with HOBr, it is assumed that the acyl hypobromite, formed in the first step of the HOBr and BrMA reaction, can react with an additional HOBr to give oxidation products. It was found that the initial rate of the reaction can be described by the following experimental rate law: k(BHOB)[BrMA]0[HOBr]0(2), where k(BHOB) = 5 M(-2) s(-1). A reaction scheme for the oxidation of BrMA by HOBr is given for conditions where HOBr is in excess. Model calculations illustrate qualitatively that the suggested reaction schemes are able to mimic the experiments. (More quantitative simulations are prevented by kinetic data missing for the various carbocation intermediates.) Finally, the effects of these newly observed reactions on oscillatory BZ systems are discussed briefly.     

Effect of dissolved oxygen on the oxidation of dithionate ion. Extremely unusual kinetic traces

The effect of dissolved oxygen on the acid-dependent disproportionation of dithionate ion (S(2)O(6)(2-)) and its oxidation with a number of reagents (I(2), Br(2), I(3)(-), Br(3)(-), IO(3)(-), BrO(3)(-), IO(4)(-), MnO(4)(-), Cr(VI), Ce(VI), and H(2)O(2)) were studied. Dithionate ion is remarkably inert at room temperature, and heating to elevated temperatures (50-90 degrees C) was necessary to observe detectable reaction rates in all of these processes. It was confirmed that dithionate ion is never oxidized directly; its redox reactions are zeroth-order with respect to the oxidizing agent and proceed through disproportionation and subsequent fast oxidation of the sulfur(IV) formed. The effect of dissolved oxygen is attributable to its reaction with sulfur(IV) produced in the disproportionation. This autoxidation occurs only with a catalyst. Cerium(III) and iodide ions were shown to catalyze the autoxidation, and their effect on the kinetic traces was studied. In a few cases, highly unusual kinetic traces, such as straight lines with sharp break points, inverted parabolas, and a combination of these, were detected and successfully interpreted in terms of simple kinetic and stoichiometric considerations.     

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-.     

Theoretical investigation of product channels in the CH3O2 + Br reaction

Several reaction pathways on the potential energy surface (PES) for the reaction of CH3O2 radicals with Br atoms are examined using both ab initio and density functional methods. Analysis of the PES suggests the presence of the stable intermediates CH3OOBr and CH3OBrO. CH3OOBr is calculated to be more stable than CH3OBrO by 9.7 kcal mol(-1) with a significant barrier preventing formation of CH3OBrO via isomerization of CH3OOBr. The relative importance of bi- and termolecular product channels resulting from the initially formed CH3OOBr adduct are assessed based on calculated barriers to the formation of CH2OO + HBr, CH3O + BrO, CH3Br + O2, and CH2O + HOBr.     

BrO与CH3SH反应机理的量子化学及拓扑研究

利用密度泛函和电子密度拓扑分析方法对BrO与CH₃SH反应的微观机理进行了理论研究. 在B3LYP/6-311G (d, p)水平上对反应势能面上的各驻点进行几何构型的全优化; 振动分析和IRC计算证实了中间体和过渡态的真实性和相互连接关系; 计算得到了各反应通道的活化能, 并进行了零点能校正. 计算结果表明: 该反应存在7个反应通道, 其中生成CH₃S＋HOBr和CH₃SO＋HBr的通道为主要反应通道. 通过对反应过程中部分驻点的电子密度拓扑分析, 首次发现了接近平面的四元环状过渡态, 从而拓展了原来对环状结构过渡态定义的适用范围.     

Ab initio studies on Al(+)(H(2)O)(n), HAlOH(+)(H(2)O)(n-1), and the size-dependent H(2) elimination reaction

We report computational studies on Al(+)(H(2)O)(n), and HAlOH(+)(H(2)O)(n-1), n = 6-14, by the density functional theory based ab initio molecular dynamics method, employing a planewave basis set with pseudopotentials, and also by conventional methods with Gaussian basis sets. The mechanism for the intracluster H(2) elimination reaction is explored. First, a new size-dependent insertion reaction for the transformation of Al(+)(H(2)O)(n), into HAlOH(+)(H(2)O)(n-1) is discovered for n > or = 8. This is because of the presence of a fairly stable six-water-ring structure in Al(+)(H(2)O)(n) with 12 members, including the Al(+). This structure promotes acidic dissociation and, for n > or = 8, leads to the insertion reaction. Gaussian based BPW91 and MP2 calculations with 6-31G* and 6-31G** basis sets confirmed the existence of such structures and located the transition structures for the insertion reaction. The calculated transition barrier is 10.0 kcal/mol for n = 9 and 7.1 kcal/mol for n = 8 at the MP2/6-31G** level, with zero-point energy corrections. Second, the experimentally observed size-dependent H(2) elimination reaction is related to the conformation of HAlOH(+)(H(2)O)(n-1), instead of Al(+)(H(2)O)(n). As n increases from 6 to 14, the structure of the HAlOH(+)(H(2)O)(n-1) cluster changes into a caged structure, with the Al-H bond buried inside, and protons produced in acidic dissociation could then travel through the H(2)O network to the vicinity of the Al-H bond and react with the hydride H to produce H(2). The structural transformation is completed at n = 13, coincident approximately with the onset of the H(2) elimination reaction. From constrained ab initio MD simulations, we estimated the free energy barrier for the H(2) elimination reaction to be 0.7 eV (16 kcal/mol) at n = 13, 1.5 eV (35 kcal/mol) at n = 12, and 4.5 eV (100 kcal/mol) at n = 8. The existence of transition structures for the H(2) elimination has also been verified by ab initio calculations at the MP2/6-31G** level. Finally, the switch-off of the H(2) elimination for n > 24 is explored and attributed to the diffusion of protons through enlarged hydrogen bonded H(2)O networks, which reduces the probability of finding a proton near the Al-H bond.     

Synthesis and characterization of a twin Cubane-type molybdenum-rhodium-sulfur cluster, [{Mo3RhCp*S4(H2O)7(O)}2]8+. X-ray structure of [{Mo3RhCpS4(H2O7O}2](CH3C6H4SO3)(8).14H2O

The reaction of [Mo(3)S(4)(H(2)O)(9)](4+) (1) with [(CpRhCl(2))(2)] afforded a novel rhodium-molybdenum cluster, [{Mo(3)RhCpS(4)(H(2)O)(7)(O)}(2)](8+) (2). X-ray structure analysis of [2](pts)(8).14H(2)O (pts(-) = CH(3)C(6)H(4)SO(3)(-)) has revealed the existence of a new oxo-bridged twin cubane-type core, (Mo(3)RhCpS(4))(2)(O)(2). The high affinity of the CpRh group for sulfur atoms in 1 seems to be the main driving force for this reaction. The strong Lewis acidity of the CpRh group in intermediate A, [Mo(3)RhCpS(4)(H(2)O)(9)](6+), caused a release of proton from one of the water molecules attached to the molybdenum atoms to give intermediate B, [Mo(3)RhCpS(4)(H(2)O)(8)(OH)](5+). The elimination of two water molecules from two intermediate B molecules, followed by the deprotonation reaction of hydroxo bridges, generated the twin cubane-type cluster 2. The formal oxidation states of rhodium and molybdenum atoms are the same before and after the reaction (i.e., Mo(IV)(3), Rh(III)). The Mo-O-Mo moieties in [2](pts)(8).14H(2)O are nearly linear with a bond angle of 164.3(3) degrees, and the basicity of the bridging oxygen atoms seems to be weak. For this reason, protonation at the bridging oxygen atoms does not occur even in a strongly acidic aqueous solution. The binding energy values of Mo 3d(5/2), Rh 3d(5/2), and C 1s obtained from X-ray photoelectron spectroscopy measurements for [2](pts)(8).14H(2)O are 229.8, 309.3, and 285 eV, respectively. The XPS measurements on the Rh 3d(5/2) binding energy indicate that the oxidation state of Rh is 3+. The binding energy of Mo 3d(5/2) (229.8 eV) compares with that observed for [1](pts)(4).7H(2)O (230.7 eV, Mo 3d(5/2)). A lower energy shift (0.9 eV) is observed in the binding energy of Mo 3d(5/2) for [2](pts)(8).14H(2)O. This energy shift may correspond to the coordination of an oxygen atom having a negative charge to the molybdenum atom.     

Synthesis of mixed acid anhydrides from methane and carbon dioxide in acid solvents

[reaction: see text] The reaction of CH(4) with CO(2) has been performed in anhydrous acids using VO(acac)(2) and K(2)S(2)O(8) as promoters. NMR analysis establishes that the primary product is a mixed anhydride of acetic acid and the acid solvent. In sulfuric acid, the overall reaction is CH(4) + CO(2) + SO(3) --> CH(3)C(O)-O-SO(3)H. Hydrolysis of the mixed anhydride produces acetic acid and the solvent acid. When trifluoroacetic acid is the solvent, acetic acid is primarily formed via the reaction CH(4) + CF(3)COOH --> CH(3)COOH + CHF(3).     

Electrochemical behavior and luminescent properties of a multilayer film containing mixed-addenda polyoxometalates K10H3[Eu(SiMo9W2O39)2] and tris(2,2'-bipyridine)ruthenium(II)

Inorganic-organic composite films containing the mixed-addenda heteropolytungsto-molybdate K(10)H(3)[Eu(SiMo(9)W(2)O(39))(2)]xH(2)O (abbreviated as EuSiMo(9)W(2)) and tris(2,2'-bipyridine)ruthenium(II) Ru(bpy)(2+)(3) (abbreviated as Ru(bpy)(3)) were fabricated by the layer-by-layer self-assembly method. UV-vis spectroscopy shows that the absorbance values at characteristic peaks increase linearly with the number of EuSiMo(9)W(2)/Ru(bpy)(3) bilayers, suggesting that the deposition process is linear and highly reproducible from layer to layer. The composition of the multilayer film was measured by X-ray photoelectron spectra. Atomic force microscopy presented a correspondingly uniform surface morphology and a homogeneity of the multilayer films. The film exhibited photoluminescence arising from the d-pi* metal-to-ligand transition of Ru(2+), and (5)D(0) metastable state to terminate levels in the (7)F(J) (J=0-4) ground-state multiplet transitions of Eu(3+). The film also exhibited catalytic activities toward the reduction of IO(-)(3), H(2)O(2), BrO(-)(3), NO(-)(2) and the oxidation of C(2)O(2-)(4). It may provide a novel material as bifunctional electrocatalysts and fluorescence probes in biochemistry, luminescence sensors, electroluminescent optical devices, and so on.     

Reaction of [RuIII(edta)(H2O)]- with H2O2 in aqueous solution. Kinetic and mechanistic investigation

The reaction of [Ru(III)(edta)(H(2)O)](-) (1) (edta = ethylenediaminetetraacetate) with hydrogen peroxide was studied kinetically as a function of [H(2)O(2)], temperature (5-35 degrees C) and pressure (1-1300 atm) at a fixed pH of 5.1 using stopped-flow techniques. The reaction was found to consist of two steps involving the rapid formation of a [Ru(III)(edta)(OOH)](2-) intermediate which subsequently undergoes parallel heterolytic and homolytic cleavage to produce [(edta)Ru(V)=O](-) (45%) and [(edta)Ru(IV)(OH)](-) (55%), respectively. The water soluble trap, 2,2'-azobis(3-ethylbenzithiazoline-6-sulfonate) (ABTS), was employed to substantiate the mechanistic proposal. Reactions were carried out under pseudo-first conditions for [ABTS] > [HOBr] > [1], and were monitored as a function of time for the formation of the one-electron oxidation product ABTS* (+). A detailed mechanism in agreement with the rate and activation parameters is presented, and the results are discussed with reference to data reported for the corresponding [Fe(III)(edta)(H(2)O)](-)/H(2)O(2) system.     

Thermochemistry of the hypobromous and hypochlorous acids, HOBr and HOCl

The enthalpies of formation of HOBr and HOCl have been estimated by employing coupled cluster theory in conjunction with the correlation consistent basis sets and corrections for core-valence, relativistic, and anharmonic effects. We have employed three different reactions to estimate the DeltaH(o)(f,298)(HOBr), namely, the atomization reaction and two homodesmic reactions. Our best estimation is DeltaH(o)(f,298) (HOBr) = -15.3 +/- 0.6 kcal/mol and is very likely to lie toward the more negative values. The present value is 1.4 kcal/mol lower than the widely used experimental determination of Ruscic and Berkowitz (J. Chem. Phys. 1994, 101, 7795), DeltaH(o)(f,298)(HOBr) > -13.93 +/- 0.42 kcal/mol. However, it is closer to the more recent measurement of Lock et al. (J. Phys. Chem. 1996, 100, 7972), DeltaH(o)(f,298)(HOBr) = -14.8 +/- 1 kcal/mol. In the case of HOCl we have determined DeltaH(o)(f,298)(HOCl) = -18.1 +/- 0.3 kcal/mol, just in the middle of the two experimental values proposed, -17.8 +/- 0.5 kcal/mol (JANAF), obtained from equilibrium constant measurements, and -18.36 +/- 0.03 kcal/mol (Joens, J. A. J. Phys. Chem. A 2001, 105, 11041), determined from the measurements of the Cl-OH bond energy. If our conclusions are correct, several enthalpies of formation that have been determined by experimental chemists, Orlando and Burholder (J. Phys. Chem. 1995, 99, 1143), and theoretical chemists, Lee (J. Phys. Chem. 1995, 99, 15074), need to be revised, since a larger value was used for DeltaH(o)(f,298)(HOBr). Employing the results obtained by Orlando and Burkholder for Br(2)O we propose DeltaH(o)(f,298)(Br(2)O) = 24.9 +/- 0.6 kcal/mol, and employing Lee's enthalpies of reaction we propose the following DeltaH(o)(f,298): for BrBrO, HBrO, ClOBr, ClBrO, BrClO, BrCN, BrNC, BrNO, BrON, FOBr, and FBrO, 39.5 +/- 1, 41.0 +/- 1, 22.7 +/- 1.5, 34.2 +/- 1.5, 40.9 +/- 1.5, 43.7 +/- 1.5, 80.1 +/- 1.5, 22.3 +/- 1, 46.2 +/- 1, 17.3 +/- 1.5, and 6.3 +/- 1.5 kcal/mol, respectively. We expect that this work will stimulate new experimental measurements of the thermodynamic properties of HOBr and HOCl.     

Vanadium complexes of the N(CH2CH2S)3(3-) and O(CH2CH2S)2(2-) ligands with coligands relevant to nitrogen fixation processes

Vanadium(III) and vanadium(V) complexes derived from the tris(2-thiolatoethyl)amine ligand [(NS3)3-] and the bis(2-thiolatoethyl)ether ligand [(OS2)2-] have been synthesized with the aim of investigating the potential of these vanadium sites to bind dinitrogen and activate its reduction. Evidence is presented for the transient existence of (V(NS3)(N2)V(NS3), and a series of mononuclear complexes containing hydrazine, hydrazide, imide, ammine, organic cyanide, and isocyanide ligands has been prepared and the chemistry of these complexes investigated. [V(NS3)O] (1) reacts with an excess of N2H4 to give, probably via the intermediates (V(NS3)(NNH2) (2a) and (V(NS3)(N2)V(NS3) (3), the V(III) adduct [V(NS3)(N2H4)] (4). If 1 is treated with 0.5 mol of N2H4, 0.5 mol of N2 is evolved and green, insoluble [(V(NS3))n] (5) results. Compound 4 is converted by disproportionation to [V(NS3)(NH3)] (6), but 4 does not act as a catalyst for disproportionation of N2H4 nor does it act as a catalyst for its reduction by Zn/HOC6H3Pri2-2,6. Compound 1 reacts with NR1(2)NR2(2) (R1 = H or SiMe3; R2(2) = Me2, MePh, or HPh) to give the hydrazide complexes [V(NS3)(NNR2(2)] (R2(2) = Me2, 2b; R2(2) = MePh, 2c; R2(2) = HPh, 2d), which are not protonated by anhydrous HBr nor are they reduced by Zn/HOC6H3Pri2-2,6. Compound 2b can also be prepared by reaction of [V(NNMe2)(dipp)3] (dipp = OC6H3Pri2-2,6) with NS3H3. N2H4 is displaced quantitatively from 4 by anions to give the salts [NR3(4)][V(NS3)X] (X = Cl, R3 = Et, 7a; X = Cl, R3 = Ph, 7b; X = Br, R3 = Et, 7c; X = N3, R3 = Bu(n), 7d; X = N3, R3 = Et, 7e; X = CN, R3 = Et, 7f). Compound 6 loses NH3 thermally to give 5, which can also be prepared from [VCl3(THF)3] and NS3H3/LiBun. Displacement of NH3 from 6 by ligands L gives the adducts [V(NS3)(L)] (L = MeCN, nu CN 2264 cm-1, 8a; L = ButNC, nu NC 2173 cm-1, 8b; L = C6H11NC, nu NC 2173 cm-1, 8c). Reaction of 4 with N3SiMe3 gives [V(NS3)(NSiMe3)] (9), which is converted to [V(NS3)(NH)] (10) by hydrolysis and to [V(NS3)(NCPh3)] (11) by reaction with ClCPh3. Compound 10 is converted into 1 by [NMe4]OH and to [V(NS3)NLi(THF)2] (12) by LiNPri in THF. A further range of imido complexes [V(NS3)(NR4)] (R4 = C6H4Y-4 where Y = H (13a), OMe (13b), Me (13c), Cl (13d), Br (13e), NO2 (13f); R4 = C6H4Y-3, where Y = OMe (13g); Cl (13h); R4 = C6H3Y2-3,4, where Y = Me (13i); Cl (13j); R4 = C6H11 (13k)) has been prepared by reaction of 1 with R4NCO. The precursor complex [V(OS2)O(dipp)] (14) [OS2(2-) = O(CH2CH2S)2(2-)] has been prepared from [VO(OPri)3], Hdipp, and OS2H2. It reacts with NH2NMe2 to give [V(OS2)(NNMe2)(dipp)] (15) and with N3SiMe3 to give [V(OS2)(NSiMe3)(dipp)] (16). A second oxide precursor, formulated as [V(OS2)1.5O] (17), has also been obtained, and it reacts with SiMe3NHNMe2 to give [V(OS2)(NNMe2)(OSiMe3)] (18). The X-ray crystal structures of the complexes 2b, 2c, 4, 6, 7a, 8a, 9, 10, 13d, 14, 15, 16, and 18 have been determined, and the 51V NMR and other spectroscopic parameters of the complexes are discussed in terms of electronic effects.