The kinetics and mechanism of peroxymonocarbonate (HCO(4)(-)) formation in the reaction of hydrogen peroxide with bicarbonate have been investigated for the pH 6-9 range. A double pH jump method was used in which (13)C-labeled bicarbonate solutions are first acidified to produce (13)CO(2) and then brought to higher pH values by addition of base in the presence of hydrogen peroxide. The time evolution of the (13)C NMR spectrum was used to establish the competitive formation and subsequent equilibration of bicarbonate and peroxymonocarbonate following the second pH jump. Kinetic simulations are consistent with a mechanism for the bicarbonate reaction with peroxide in which the initial formation of CO(2) via dehydration of bicarbonate is followed by reaction of CO(2) with H(2)O(2) (perhydration) and its conjugate base HOO(-) (base-catalyzed perhydration). The rate of peroxymonocarbonate formation from bicarbonate increases with decreasing pH because of the increased availability of CO(2) as an intermediate. The selectivity for formation of HCO(4)(-) relative to the hydration product HCO(3)(-) increases with increasing pH as a consequence of the HOO(-) pathway and the slower overall equilibration rate, and this pH dependence allows estimation of rate constants for the reaction of CO(2) with H(2)O(2) and HOO(-) at 25 °C (2 × 10(-2) M(-1) s(-1) and 280 M(-1) s(-1), respectively). The contributions of the HOO(-) and H(2)O(2) pathways are comparable at pH 8. In contrast to the perhydration of many other common inorganic and organic acids, the facile nature of the CO(2)/HCO(3)(-) equilibrium and relatively high equilibrium availability of the acid anhydride (CO(2)) at neutral pH allows for rapid formation of the peroxymonocarbonate ion without strong acid catalysis. Formation of peroxymonocarbonate by the reaction of HCO(3)(-) with H(2)O(2) is significantly accelerated by carbonic anhydrase and the model complex [Zn(II)L(H(2)O)](2+) (L = 1,4,7,10-tetraazacyclododecane).

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.

A new divalent cadmium phosphonate, Cd2Cl2(H2O)4(H2L), has been synthesized from the ethylenediamine-N,N'-bis(methylenephosphonic acid) (H4L). The obtained microcrystalline compound has been characterized by solid-state IR spectra and 13C, 31P, and 113Cd CP MAS NMR. The static 13P NMR spectra have been also recorded to give the delta11, delta22, and delta33 chemical shift parameters for both compounds. The spectral data, collected for Cd2Cl2(H2O)4(H2L), are in an agreement with its X-ray powder diffraction structure solved with the cell dimensions a = 16.6105(10), b = 7.1572(4), and c = 6.8171(4) A and beta = 98.327(4) degrees. The octahedral coordination sphere of the cadmium atoms consists of two phosphonate oxygen atoms, two water oxygen atoms, and the two chlorine atoms. Cadmium atoms are bridged by the chlorine atoms forming four-membered rings. The phosphorus atoms exhibit a tetrahedral coordination with two oxygen atoms bonded to the cadmium atoms with P-O distances of 1.503(10) and 1.504(10) A. The third oxygen atom, showing a longer P-O distance (1.546(9) A), is not bonded to the metal center, nor is it bonded to a proton. The combined IR and NMR proton-phosphorus cross-polarization kinetic data together with the X-ray data confirm that the cadmium phosphonate has the zwitterionic structure (NH2(+)CH2P(O2Cd2)O-) similar to the initial aminophosphonic acid H4L.

Combining variable-temperature infrared and NMR spectroscopic studies with quantum-chemical calculations (density functional theory (DFT) and natural bond orbital) allowed us to address the problem of competition between MH (M = transition metal) and BH hydrogens as proton-accepting sites in dihydrogen bond (DHB) and to unravel the mechanism of proton transfer to complex (PP3)RuH(η(1)-BH4) (1, PP3 = κ(4)-P(CH2CH2PPh2)3). Interaction of complex 1 with CH3OH, fluorinated alcohols of variable acid strength [CH2FCH2OH, CF3CH2OH, (CF3)2CHOH (HFIP), (CF3)3COH], and CF3COOH leads to the medium-strength DHB complexes involving BH bonds (3-5 kcal/mol), whereas DHB complexes with RuH were not observed experimentally. The two proton-transfer pathways were considered in DFT/M06 calculations. The first one goes via more favorable bifurcate complexes to BHterm and high activation barriers (38.2 and 28.4 kcal/mol in case of HFIP) and leads directly to the thermodynamic product [(PP3)RuHeq(H2)](+)[OR](-). The second pathway starts from the less-favorable complex with RuH ligand but shows a lower activation barrier (23.5 kcal/mol for HFIP) and eventually leads to the final product via the isomerization of intermediate [(PP3)RuHax(H2)](+)[OR](-). The B-Hbr bond breaking is the common key step of all pathways investigated.

The reaction of zinc chloride with 1,2-ethanediylbis(iminomethylene)bis(phosphonic acid) in acidic conditions yielded dichloro[1,2-ethanediylbis(iminomethylene)bis(phosphonato)]trizinc dihydrate, Zn 3 Cl 2 (HO 3 PCH 2 NHCH 2 CH 2 NHCH 2 -PO 3 H) 2 ·2 H 2 O which crystallizes in the monoclinic system and space group P2 1 /n, with the unit cell parameters a = 9.94316(4), b = 10.44577(5), c = 24.3240(1) Å, β = 90.003(1)°, and Z = 4. The crystal structure was determined ab initio

The oxidation of dihydronicotinamide adenine dinucleotide (NADH) by chlorine dioxide in phosphate buffered solutions (pH 6-8) is very rapid with a second-order rate constant of 3.9 x 10(6) M(-1) s(-1) at 24.6 degrees C. The overall reaction stoichiometry is 2ClO2(*) per NADH. In contrast to many oxidants where NADH reacts by hydride transfer, the proposed mechanism is a rate-limiting transfer of an electron from NADH to ClO2(*). Subsequent sequential fast reactions with H(+) transfer to H2O and transfer of an electron to a second ClO2(*) give 2ClO2(-), H3O(+), and NAD(+) as products. The electrode potential of 0.936 V for the ClO2(*)/ClO2(-) couple is so large that even 0.1 M of added ClO2(-) (a 10(3) excess over the initial ClO2(*) concentration) fails to suppress the reaction rate.

The cover picture shows the richness of 1,2-ethanediylbis-(iminomethylene)bis(phosphonic acid) (H 4 L) used as a ligand. The left compound is cadmium phosphonate, Cd 2 Cl 2 (H 2 O) 4 (H 2 L), in which the Cd atoms form dimers through bridging chloride ions. These dimers are, in turn, formed into rows by the phosphonate groups, and the rows are crosslinked by the organic chain of the ligand into layers. The second picture shows Zn 3 Cl 2 (H 2 L) 2 ⋅2H 2 O, in which Zn atoms are tetrahedrally coordinated. One of the Zn atoms lies in rows parallel to the b-axis, which are sandwiched between rows formed by the two other Zn atoms. The carbonϪnitrogen chains crisscross each other forming a three-dimensional structure. The structure of this latest compound is presented in the article by A. Clearfield et al. on p. 829 ff.