A kinetic and thermodynamic study of the unexpected comproportionation reaction between cis-[Os(VIII)O4(OH)2](2-) and trans-[Os(VI)O2(OH)4](2-) to form a postulated [Os(VII)O3(OH)3](2-) complex anion

A kinetic study of [OsO(4)] reduction by aliphatic alcohols (MeOH and EtOH) was performed in a 2.0 M NaOH matrix at 298.1 K. The rate model that best fitted the UV-VIS data supports a one-step, two electron reduction of Os(VIII) (present as both the [Os(VIII)O(4)(OH)](-) and cis-[Os(VIII)O(4)(OH)(2)](2-) species in a ratio of 0.34:0.66) to form the trans-[Os(VI)O(2)(OH)(4)](2-) species. The formed trans-[Os(VI)O(2)(OH)(4)](2-) species subsequently reacts relatively rapidly with the cis-[Os(VIII)O(4)(OH)(2)](2-) complex anion to form a postulated [Os(VII)O(3)(OH)(3)](2-) species according to: cis-[Os(VIII)O(4)(OH)(2)](2-) + trans-[Os(VI)O(2)(OH)(4)](2-) (k+2) (k-2) 2[Os(VII)O(3)(OH)(3)](2-). The calculated forward, k(+2), and reverse, k(-2), reaction rate constants of this comproportionation reaction are 620.9 ± 14.6 M(-1) s(-1) and 65.7 ± 1.2 M(-1) s(-1) respectively. Interestingly, it was found that the postulated [Os(VII)O(3)(OH)(3)](2-) complex anion does not oxidize MeOH or EtOH. Furthermore, the reduction of Os(VIII) with MeOH or EtOH is first order with respect to the aliphatic alcohol concentration. In order to corroborate the formation of the [Os(VII)O(3)(OH)(3)](2-) species predicted with the rate model simulations, several Os(VIII)/Os(VI) mole fraction and mole ratio titrations were conducted in a 2.0 M NaOH matrix at 298.1 K under equilibrium conditions. These titrations confirmed that the cis-[Os(VIII)O(4)(OH)(2)](2-) and trans-[Os(VI)O(2)(OH)(4)](2-) species react in a 1:1 ratio with a calculated equilibrium constant, K(COM), of 9.3 ± 0.4. The ratio of rate constants k(+2) and k(-2) agrees quantitatively with K(COM), satisfying the principle of detailed balance. In addition, for the first time, the molar extinction coefficient spectrum of the postulated [Os(VII)O(3)(OH)(3)](2-) complex anion is reported.     

The extraction of Zn(II), Cd(II) and Pb(II) from hydrochloric acid media by amberlite LA-2 hydrochloride dissolved in 1,2-dichloroethane

The extraction of HC1 by the secondary amine (B), known as Amberlite LA-2, dissolved in 1,2-dichloroethane and the aggregation of BHC1 have been studied by using a two-phase potentiometric titration technique. The experimental data, treated by a general minimizing program, indicate dimerization: 2 BHClright harpoon over left harpoon(BHCl)(2). The equilibrium constant of this reaction was calculated. The extraction of ZnCl(2), CdCl(2) and PbCl(2) from 0.2,0.5, 1.0 and 2.0M HCl, and 1MNaCl by Amberlite LA-2 hydrochloride (BHCl), dissolved in 1,2-dichloroethane, has been studied. The complexes (BHCl)(2)ZnCl(2), (BHCl)(2)CdCl(2) and (BHCl)(2)PbCl(2) were found to exist, irrespective of the composition of the aqueous phase. The formation constant of the first was calculated.     

Enantiomer recognition of amides by dirhodium(II) tetrakis[methyl 2-oxopyrrolidine-5(S)-carboxylate

Association constants of the chiral dirhodium(II) carboxamidate Rh(2)(5S-MEPY)(4) with Lewis bases including acetonitrile and amides have been determined by UV-vis titration experiments. With chiral lactams and acyclic acetamides in their R- and S-configurations equilibrium constants with chiral dirhodium carboxamidates are measures of chiral differentiation, and equilibrium constant ratios as high as three have been determined. From equilibrium associations with acetamide, N-methylacetamide, and N,N-dimethylacetamide, as well as equilibrium constants for lactams and acyclic amides, higher values occur when both the amide carbonyl oxygen and N-H are bound to Rh(2)(5S-MEPY)(4). This cooperative bonding mode is confirmed by NMR measurements that show a distinctive shift of a N-H absorption, as well as perturbation of the ligands on dirhodium compound, and they suggest N-H association with a ligated oxygen of Rh(2)(5S-MEPY)(4). Measurements were made on the dirhodium(II) compound from which protective axial ligands have been removed to enhance their reliability.     

Reversible oxidation state change in germanium(tetraphenylporphyrin) induced by a dative ligand: aromatic GeII(TPP) and antiaromatic GeIV(TPP)(pyridine)2

Treatment of GeCl2(dioxane) with Li2(TPP)(OEt2)2 (TPP = tetraphenylporphyrin) in THF yields Ge(TPP), the first free Ge(II) porphyrin complex. In pyridine Ge(TPP) is converted to Ge(TPP)(py)2, an antiaromatic Ge(IV) complex, whereas in benzene the reaction is reversed, and pyridine dissociates from Ge(TPP)(py)2 to form Ge(TPP). That reversible reaction represents an unusual, if not unique, example of an oxidation-state change in a metal induced by coordination of a dative ligand. UV-vis and 1H NMR spectroscopy show that Ge(TPP) is an aromatic Ge(II) porphyrin complex, while the 1H NMR spectrum of Ge(TPP)(py)2 clearly indicates the presence of a strong paratropic ring current, characteristic of an antiaromatic compound. Both Ge(TPP) and Ge(TPP)(py)2 have been crystallographically characterized, and the antiaromaticity of Ge(TPP)(py)2 leads to alternating short and long C-C bonds along the 20-carbon periphery of its porphine ring system. Coordination of pyridine to Ge(TPP) greatly increases its reducing ability: the Ge(TPP)0/2+ redox potential is about +0.2 V, while the Ge(TPP)(py)2(0/+) redox potential is -1.24 V (both vs. ferrocene). The equilibrium constant of the reaction Ge(TPP) + 2 py = Ge(TPP)(py)2 in C6D6 is 22 M-2. The germanium complex of the more electron-withdrawing tetrakis[3,5-bis(trifluoromethyl)phenyl]porphyrin, Ge(TArFP), and its pyridine adduct Ge(TArFP)(py)2 were synthesized. The equilibrium constant of the reaction Ge(TArFP) + 2 py = Ge(TArFP)(py)2 in C6F6/C6D6 is 2.3 x 10(4) M-2. Density functional theory calculations are consistent with the experimental observation that M(TPP)(py)2 formation from M(TPP) and pyridine is most favorable for M=Si, borderline for Ge, and unfavorable for Sn.     

Kinetic and equilibria studies of the aquation of the trinuclear platinum phase II anticancer agent [(trans-PtCl(NH(3))(2))(2)(mu-trans-Pt(NH(3))(2)(NH(2)(CH(2))(6)NH(2))(2))](4+) (BBR3464)

The hydrolysis profile of the bifunctional trinuclear phase II clinical agent [(trans-PtCl(NH(3))(2))(2)(mu-trans-Pt(NH(3))(2)(NH(2)(CH(2))(6)NH(2))(2))](4+) (BBR3464, 1) has been examined using [(1)H,(15)N] heteronuclear single quantum coherence (HSQC) 2D NMR spectroscopy. Reported are estimates of the rate and equilibrium constants for the first and second aquation steps, together with the acid dissociation constant (pK(a1) approximately equal to pK(a2) approximately equal to pK(a3)). The equilibrium constants for the aquation determined by NMR at 298 and 310 K (I = 0.1 M, pH 5.3) are similar, pK(1) = pK(2) = 3.35 +/- 0.04 and 3.42 +/- 0.04, respectively. At lower ionic strength (I = 0.015 M, pH 5.3) the values at 288, 293, and 298 K are pK(1) = pK(2) = 3.63 +/- 0.05. This indicates that the equilibrium is not strongly ionic strength or temperature dependent. The aquation and anation rate constants for the two-step aquation model at 298 K in 0.1 M NaClO(4) (pH 5.3) are k(1) = (7.1 +/- 0.2) x 10(-5) s(-1), k(-1) = 0.158 +/- 0.013 M(-1) s(-1), k(2) = (7.1 +/- 1.5) x 10(-5) s(-1), and k(-2) = 0.16 +/- 0.05 M(-1) s(-1). The rate constants in both directions increase 2-fold with an increase in temperature of 5 K, and rate constants increase with a decrease in solution ionic strength. A pK(a) value of 5.62 plus minus 0.04 was determined for the diaqua species [(trans-Pt(NH(3))(2)(OH(2)))(2)(mu-trans-Pt(NH(3))(2)(NH(2)(CH(2))(6)-NH(2))(2))](6+) (3). The speciation profile of 1 under physiological conditions is explored and suggests that the dichloro form predominates. The aquation of 1 in 15 mM phosphate was also examined. No slowing of the initial aquation was observed, but reversible reaction between aquated species and phosphate does occur.     

Bis(acetylacetonato)ruthenium(II) complexes containing alkynyldiphenylphosphines. Formation and redox behaviour of [Ru(acac)2(Ph2PC triple bond CR)2] (R=H, Me, Ph) complexes and the binuclear complex cis-[{Ru(acac)2}2(micro-Ph2PC triple bond CPPh2)}2

Two equivalents of Ph(2)PC triple bond CR (R=H, Me, Ph) react with thf solutions of cis-[Ru(acac)(2)(eta(2)-alkene)(2)] (acac=acetylacetonato; alkene=C(2)H(4), 1; C(8)H(14), 2) at room temperature to yield the orange, air-stable compounds trans-[Ru(acac)(2)(Ph(2)PC triple bond CR)(2)] (R=H, trans-3; Me=trans-4; Ph, trans-5) in isolated yields of 60-98%. In refluxing chlorobenzene, trans-4 and trans-5 are converted into the yellow, air-stable compounds cis-[Ru(acac)(2)(Ph(2)PC triple bond CR)(2)] (R=Me, cis-4; Ph, cis-5), isolated in yields of ca. 65%. From the reaction of two equivalents of Ph(2)PC triple bond CPPh(2) with a thf solution of 2 an almost insoluble orange solid is formed, which is believed to be trans-[Ru(acac)(2)(micro-Ph(2)PC triple bond CPPh(2))](n) (trans-6). In refluxing chlorobenzene, the latter forms the air-stable, yellow, binuclear compound cis-[{Ru(acac)(2)(micro-Ph(2)PC triple bond CPPh(2))}(2)] (cis-6). Electrochemical studies indicate that cis-4 and cis-5 are harder to oxidise by ca. 300 mV than the corresponding trans-isomers and harder to oxidise by 80-120 mV than cis-[Ru(acac)(2)L(2)] (L=PPh(3), PPh(2)Me). Electrochemical studies of cis-6 show two reversible Ru(II/III) oxidation processes separated by 300 mV, the estimated comproportionation constant (K(c)) for the equilibrium cis-6(2+) + cis6 <=> 2(cis-6(+)) being ca. 10(5). However, UV-Vis spectra of cis-6(+) and cis-6(2+), generated electrochemically at -50 degrees C, indicate that cis-6(+) is a Robin-Day Class II mixed-valence system. Addition of one equivalent of AgPF(6) to trans-3 and trans-4 forms the green air-stable complexes trans-3 x PF(6) and trans-4 x PF(6), respectively, almost quantitatively. The structures of trans-4, cis-4, trans-4 x PF(6) and cis-6 have been confirmed by X-ray crystallography.     

Proton transfer to nickel-thiolate complexes. 1. Protonation of [Ni(SC(6)H(4)R-4)(2)(Ph(2)PCH(2)CH(2)PPh(2))] (R = Me, MeO, H, Cl, or NO(2))

The kinetics of the equilibrium reaction between [Ni(SC(6)H(4)R-4)(2)(dppe)] (R= MeO, Me, H, Cl, or NO(2); dppe = Ph(2)PCH(2)CH(2)PPh(2)) and mixtures of [lutH](+) and lut (lut = 2,6-dimethylpyridine) in MeCN to form [Ni(SHC(6)H(4)R-4)(SC(6)H(4)R-4)(dppe)](+) have been studied using stopped-flow spectrophotometry. The kinetics for the reactions with R = MeO, Me, H, or Cl are consistent with a single-step equilibrium reaction. Investigation of the temperature dependence of the reactions shows that DeltaG = 13.6 +/- 0.3 kcal mol(-)(1) for all the derivatives but the values of DeltaH and DeltaS vary with R (R = MeO, DeltaH() = 8.5 kcal mol(-)(1), DeltaS = -16 cal K(-)(1) mol(-)(1); R = Me, DeltaH() = 10.8 kcal mol(-)(1), DeltaS = -9.5 cal K(-)(1) mol(-)(1); R = Cl, DeltaH = 23.7 kcal mol(-)(1), DeltaS = +33 cal K(-)(1) mol(-)(1)). With [Ni(SC(6)H(4)NO(2)-4)(2)(dppe)] a more complicated rate law is observed consistent with a mechanism in which initial hydrogen-bonding of [lutH](+) to the complex precedes intramolecular proton transfer. It seems likely that all the derivatives operate by this mechanism, but only with R = NO(2) (the most electron-withdrawing substituent) does the intramolecular proton transfer step become sufficiently slow to result in the change in kinetics. Studies with [lutD](+) show that the rates of proton transfer to [Ni(SC(6)H(4)R-4)(2)(dppe)] (R = Me or Cl) are associated with negligible kinetic isotope effect. The possible reasons for this are discussed. The rates of proton transfer to [Ni(SC(6)H(4)R-4)(2)(dppe)] vary with the 4-R-substituent, and the Hammett plot is markedly nonlinear. This unusual behavior is attributable to the electronic influence of R which affects the electron density at the sulfur.     

Insertion reactions of trans-Mo(dmpe)2(H)(NO) with imines

The insertion chemistry of the hydride complex trans-Mo(dmpe)(2)(H)(NO) (1) (dmpe = bis(dimethylphosphino)ethane) with imines has been investigated. It was found that disubstituted aromatic imines RCH[double bond]NR' (R, R' = Ar) insert into the Mo-H bond of 1, while a series of various mono- and other disubstituted imines do not react. The insertion products trans-Mo(dmpe)(2)(NO)[NR'(CH(2)R)] (R = R' = Ph (2); R = Cp(2)Fe, R' = Ph (3); R = Ph, R' = Cp(2)Fe (4); R = 1-naphthyl, R' = Ph (5)) have been isolated and fully characterized by elemental analysis, IR and NMR spectroscopy, and mass spectrometry. The imine PhCH[double bond]NC(10)H(7) (C(10)H(7) = 1-naphthyl) reacted with 1 establishing an equilibrium to produce the nonisolable complex trans-Mo(dmpe)(2)(NO)[NC(10)H(7)(CH(2)Ph)] (6). The equilibrium constant for this reaction has been derived from VT-NMR measurements, and the Delta H and Delta S values of this reaction were calculated to be -48.8 +/- 0.4 kJ.mol(-1) and -33 +/- 1 J.K(-1).mol(-1) reflecting a mild exothermic process and its associative nature. Single-crystal X-ray diffraction analyses were carried out on 2-5.     

Studies on metal carbonate equilibria-part 21 Study of the U(VI)H(2)OCO(2)(g) system by thermal lensing spectrophotometry

Equilibria in the U(VI)H(2)OCO(2)(g) system in 0.5M sodium perchlorate medium at 25 degrees have been studied. By using thermal tensing spectrophotometry (TLS) and a very low total concentration of U(V1) (4 x 10(-6)M) information could be obtained on equilibria involving UO(2)(CO(3))(2-)(2) without complications due to formation of the trimer (UO(2))(3)(CO(3))(6-)(6). The experimental data allowed a precise determination of the equilibrium constant log K(3) = 6.35 +/- 0.05 for the reaction UO(2)(CO(3))(2-)(2) + CO(2-)(3) right harpoon over left harpoonright harpoon over left harpoon UO(2)(CO(3))(4-)(3). The interpretation of TLS data is briefly discussed, as well as the potential use of this technique for studies of the speciation of trace elements in natural water systems.     

Structure and Thermodynamics of NaF-AlF(3) Melts with Addition of CaF(2) and MgF(2)

The NaF-AlF(3) system with additions of CaF(2) and MgF(2) has been studied with Raman and vapor pressure measurements for 3 >/= CR (NaF/AlF(3) molar ratio) >/= 1 and up to 50 mol % additive. The results show that the binary melt can be described using the two equilibria AlF(6)(3)(-) = AlF(6)(2)(-) + F(-) and AlF(5)(2)(-) = AlF(4)(-) + F(-) with equilibrium constants 0.25 and 0.05, respectively, at 1293 K. Both reactions have positive reaction enthalpies. The first equilibrium is strongly shifted to the right resulting in a melt mixture with very low AlF(6)(3)(-) concentrations even at the Na(3)AlF(6) composition. Evidence for nonideal mixing of anions was found. For the ternaries, models based on Raman data are presented and compared with vapor pressure measurements. Good agreement is observed when association between the additives, CaF(2) or MgF(2), with the AlF(5)(2)(-) ions in the melt was considered. This association could be experimentally observed through a band broadening and a slight shift in the AlF(5)(2)(-) band frequency. Our vapor pressures and Raman data both indicate that MgF(2) clearly acts as an acid when added to NaF-AlF(3) melts of any composition. When CaF(2) is added, a slight decrease of vapor pressure occurs. Raman data indicate a decrease of AlF(4)(-) concentration, corresponding to a dissociation of CaF(2) with liberation of F(-) ions. All these results are, however, very much dependent on the initial melt composition. These data are explained in terms of acid-base, dilution, and association reactions of the solute with the solvent.     

Kinetics and mechanism of phosphine autoxidation catalyzed by imidorhenium(V) complexes

The relative binding abilities of PY(3) (PMe(3), PMe(2)Ph, PMePh(2), PPh(3), P(OMe)(3), P(OMe)(2)Ph, PEt(3), P(OEt)(3), P(OEt)Ph(2), and dmpe) toward Re(V) were evaluated. The equilibrium constants for the reactions, MeRe(NAr)(2)[P(OMe)(3)](2) + PY(3) = MeRe(NAr)(2)(PY(3))(2) (1) + P(OMe)(3), decrease in the order PMe(3) > dmpe > PMe(2)Ph > P(OMe)(2)Ph approximately PEt(3) > P(OEt)(3) > PMePh(2) > P(OEt)Ph(2) > PPh(3). Both electronic and steric factors contribute to this trend. The equilibrium constant increases as the basicity of PY(3) increases when the steric demand is the same. However, steric effects play a major role in the coordination, and this is the reason that the affinity of PEt(3) toward Re(V) is less than that of PMe(2)Ph. A mixed-ligand complex, MeRe(NAr)(2)[P(OMe)(3)](PY(3)), was also observed in the course of the stepwise formation of 1. The large coupling constant, (2)J(PP) > or = 491 Hz, between the two phosphorus atoms suggests a trans geometry for the phosphines. Compound 1 catalyzes the oxidation of PY(3) by molecular oxygen. Kinetic studies suggest that the reaction of 1 with O(2) is first-order with respect to [O(2)] and inverse-first-order with respect to [PY(3)]. A mechanism involving a peroxorhenium intermediate MeRe(NAr)(2)(eta(2)-O(2)) is proposed for the catalytic processes. The reactivity of MeRe(NAr)(2)(eta(2)-O(2)) toward triaryl phosphines parallels that of the known compound MeReO(2)(eta(2)-O(2)).     

Surface Complexation Modeling of K(+), NO(3)(-), SO(4)(2-), Ca(2+), F(-), Co(2+), and Cr(3+) Ion Adsorption on Silica Gel

Surface complex formation of K(+), NO(3)(-), SO(4)(2-), Ca(2+), F(-), Co(2+), and Cr(3+) ions was determined on the surface of silica gel. Experimental data obtained by acid-base titration of suspensions were interpreted in terms of the triple-layer model. The value of the deprotonation constant of surface OH could be determined precisely but the protonation constant was rather uncertain. The logarithms of ion pair formation constants for K(+), NO(3)(-), Ca(2+), and SO(4)(2-) adsorbed in the beta-plane are log K(ipM,X) approximately 0, therefore these species can be considered inert ions in the investigated pH range. F(-), Co(2+), and Cr(3+) ions were found to be strongly sorbed in the o-plane. In order to provide a good fit and to obtain parameters independent of their initial values, all possible equilibrium must be accounted for in the models. Copyright 2001 Academic Press.     

Synthesis of [NH(4)]MnCl(2)(OAc) and [NH(4)](2)MnCl(4)(H(2)O)(2) by solvothermal dehydration and structure/property correlations in a one-dimensional antiferromagnet

The utility of the solvothermal dehydration strategy whereby superheated acetonitrile reacts with water of hydration to form ammonium acetate is demonstrated in the synthesis of [NH(4)]MnCl(2)(OAc), I, and [NH(4)](2)MnCl(4)(H(2)O)(2), II, from MnCl(2).4H(2)O. The structure of I is shown to crystallize in the monoclinic space group C2/c (No. 15) with a = 15.191(6) A, b = 7.044(2) A, c = 13.603(6) A, beta = 107.31 degrees, V = 1389.7(9) cm(-)(1), and Z = 8. The structure of II crystallizes in the space group I4/mmm (No. 139) with a = 7.5250(5) A, b = 8.276(2) A, V = 468.6(1) cm(-)(1), and Z = 2. Both structures exhibit extensive hydrogen bonding that controls both local Mn-Cl bonding and the interchain organization. I is shown to be a one-dimensional Heisenberg antiferromagnet with an intrachain exchange constant J/k = -2.39 K. This structure exhibits exchange coupling intermediate between the well-studied triply and doubly chloride-bridged one-dimensional manganese Heisenberg antiferromagnets. The structure/property correlation demonstrates a linear dependence of the exchange constant on the Mn-Cl-Mn bond angle, alpha, for alpha < 94 degrees.     

Solvent effects on the conversion of dicopper(II) micro-eta(2):eta(2)-peroxo to bis-micro-oxo dicopper(III) complexes: direct probing of the solvent interaction

A new tridentate ligand, PYAN, is employed to investigate solvent influences for dioxygen reactivity with [Cu(PYAN)(MeCN)]B(C(6)F(5))(4) (1). Stopped-flow kinetic studies confirm that the adducts [[u(II)(PYAN)]2)(O(2))][B(C(6)F(5))(4)](2) (2(Peroxo)) and [[u(III)(PYAN)]2)(O)(2)][B(C(6)F(5))(4)](2) (2(Oxo)) are in rapid equilibrium. Thermodynamic parameters for the equilibrium between 2(Peroxo) and 2(Oxo) re as follows: THF, deltaH degrees approximately -15.7 kJ/mol, deltaS degrees approximately -83 J/K.mol; acetone, deltaH degrees approximately -15.8 kJ/mol, deltaS degrees approximately -76 J/K.mol. UV-visible absorption and resonance Raman spectroscopic signatures demonstrate that the equilibrium is highly solvent dependent; the mixture is mostly 2(Peroxo) in CH(2)Cl(2), but there are significantly increasing quantities of 2(Oxo) along the series methylene chloride --> diethyl ether --> acetone --> tetrahydrofuran (THF). Copper(II)-N(eq) stretches (239, 243, 244, and 246 cm(-)(1) in CH(2)Cl(2), Et(2)O, acetone, and THF, respectively) are identified for 2(Peroxo), but they are not seen in 2(Oxo), revealing for the first time direct evidence for solvent coordination in the more open 2(Peroxo) structure.     

Remarkably efficient hydrolysis of methylparathion catalyzed by [2-(2-pyridyl)phenyl-C,N]palladium(II) complexes

The reaction of the palladium(II) acetate derivative [Pd(NwedgeC)(OAc)]2 (NwedgeC = (NC5H4-2-C6H4(C2,N) or (2-(2-pyridyl)-phenyl-C,N)) with methylparathion and water in THF leads to the formation of [Pd(NwedgeC)(mu-SP(=O)(OCH3)2)]2 (1), which reacts with PPh3 in THF to afford mononuclear complex [Pd(NwedgeC)(SP(=O)(OCH3)2)(PPh3)] (2). Compounds 1 and 2 have been characterized by 1H, 13C, and 31P NMR spectroscopy; elemental analysis; and single-crystal X-ray diffraction. When dissolved in water, 1 serves as a precatalyst for the hydrolysis of methylparathion. Kinetic and spectroscopic studies suggest that compound 1 dissociates in aqueous solution to afford cationic diaqua complex [Pd(NwedgeC)(OH2)2]+ (A). At basic pH, A is converted into its deprotonated form [Pd(NwedgeC)(OH2)(OH)] (B), which dimerizes to afford a dinuclear complex, presumably [Pd(NwedgeC)(mu-OH)]2 (C). At pH 7, the reaction is first order in substrate and first order in palladium catalyst A, with k2 = 146 +/- 9 M(-1) s(-1) at 303 K. At more-basic pH, the reaction rate increases and shows an apparent half-order dependence in palladium catalyst. These observations suggest that the active form of the catalyst at basic pH is B, whose concentration is controlled by an equilibrium with inactive C. Analysis of the data obtained at pH 9 yields a dimer formation constant K(f) = [C]/[B]2 = (6.6 +/- 5.6) x 10(6) M(-1) and a second-order rate constant k2 of (8.6 +/- 3.6) x 10(3) M(-1) s(-1) at 298 K. The pH dependence of the reaction rate as well as a spectroscopic titration indicates that the pKa of A is in the 9.5-9.7 range. Determination of the activation parameters at both pH 7 and 9 suggests that catalysis occurs via an associative mechanism whose rate-determining step involves the substitution of a water ligand of A by a molecule of methylparathion at neutral pH and nucleophilic attack of the phosphorus center of methylparathion by a hydroxide ligand of B at basic pH.     

Photochemical investigation of Roussin's red salt esters: Fe2(mu-SR)2(NO)4

The photochemistry of various Roussin's red ester compounds of the general formula Fe(2)(SR)(2)(NO)(4), where R = CH(3), CH(2)CH(3), CH(2)C(6)H(5), CH(2)CH(2)OH, and CH(2)CH(2)SO(3)(-), were investigated. Continuous photolyses of these ester compounds in aerated solutions led to the release of NO with moderate quantum yields for the photodecomposition of the ester (Phi(RSE) = 0.02-0.13). Electrochemical studies using an NO electrode demonstrated that 4 mol of NO are generated for each mole of ester undergoing photodecomposition. Nanosecond flash photolysis studies of Fe(2)(SR)(2)(NO)(4) (where R = CH(2)CH(2)OH and CH(2)CH(2)SO(3)(-)) indicate that the initial photoreaction is the reversible dissociation of NO. In the absence of oxygen, the presumed intermediate, Fe(2)(SR)(2)(NO)(3), undergoes second-order reaction with NO to regenerate the parent cluster with a rate constant of k(NO) = 1.1 x 10(9) M(-1) s(-1) for R = CH(2)CH(2)OH. Under aerated conditions the intermediate reacts with oxygen to give permanent photochemistry.     

Optosensing behavior of the first Ru(II)-compound of di-2-pyridylketone-p-nitrophenylhydrazone (dpknph), [Ru(bpy)2(dpknph)]Cl2

The reaction between Ru(bpy)(2)Cl(2) (bpy=2,2'-bipyridine) and di-2-pyridylketone-p-nitrophenylhydrazone (dpknph) in refluxing ethanol gave [Ru(bpy)(2)(dpknph)]Cl(2) in good yield. Optical measurements on [Ru(bpy)(2)(dpknph)]Cl(2) in non-aqueous media revealed the presence of two interlocked electronic states due to conformational changes associated with the hydrazone moiety of [Ru(bpy)(2)(dpknph)]Cl(2). The equilibrium distribution of the high-energy beta-conformation associated with the high-energy electronic state and the low-energy alpha-conformation associated with the low-energy electronic state is solvent and solute dependent controlled by the solvent-solute and solute-solute interactions. The interplay between the alpha- and beta-conformations of [Ru(bpy)(2)(dpknph)]Cl(2) allowed calculations of the extinction coefficients of electronic states by forcing the equilibrium to shift to one conformation using chemical stimuli. Extinction coefficients of 56000+/-2000 and 48500+/-2000 M(-1) cm(-1) were calculated in DMSO for the beta- and alpha-conformations of [Ru(bpy)(2)(dpknph)]Cl(2), respectively, using excess HgCl(2) in DMSO. Thermo-optical measurements on [Ru(bpy)(2)(dpknph)]Cl(2) in DMSO confirmed the interconversion between the alpha- and beta-conformations of [Ru(bpy)(2)(dpknph)]Cl(2) and gave changes in enthalpy (DeltaH(?)) of -35.5+/-4.0 and 13.0+/-0.5 kJ mol(-1), entropy (DeltaS(?)) of -126.9+/-20 and 45.2+/-4.5 kJ mol(-1), and free energy (DeltaG(?)) of 2.31+/-0.2 and -0.48+/-0.2 kJ mol(-1) in the absence and presence of NaBH(4) at 295 K. The high values for the extinction coefficients and low values and sensitivity of the activation parameters for the interconversion between the alpha- and beta-conformations of [Ru(bpy)(2)(dpknph)]Cl(2) in DMSO to solution composition allowed for the use of this system ([Ru(bpy)(2)(dpknph)]Cl(2) and surrounding solvent or solute molecules) as a spectrophotometric sensor for a variety of chemical stimuli that include metal ions. Group 12 metal ions in concentrations as low as 1.00x10(-8) M can be detected and determined using [Ru(bpy)(2)(dpknph)]Cl(2) in DMSO in the presence and absence of NaBH(4).     

Pairwise exchanges of oxo and imido groups in rhenium(VII) compounds

The kinetic and thermodynamic parameters for the oxo and imido exchange reactions among MeReO(3), MeReO(2)(NR), MeReO(NR)(2), and MeRe(NR)(3) (R = 1-adamantyl, Ad; or 2,6-diisopropylphenyl, Ar) have been measured. The rate constant for the NAr series decreases from 0.27 to 0.0024 L mol(-1) s(-1) at 25 degrees C in benzene as the total number of participating imido groups increases from 2 to 4, indicating that steric effects play an important role in the kinetics of the ligand exchange reactions. But, with NAd, the values of k/L mol(-1) s(-1) are 0.2 (4 NAd), 100 (3 NAd), and 0.74 (2 NAd). The equilibrium constants, also subject to steric effects, are much larger than those predicted by ligand combination statistics and greatly favor the mixed oxo-imido compounds. The different steric demands by imido and oxo ligands are believed to be the main factor for the larger equilibrium constants because the equilibrium constant shows minimal dependence on temperature. The large negative activation entropies for the ligand exchange reactions are consistent with a metathesis mechanism featuring nearly concurrent interchange of oxo and imido groups.     

Comprehensive kinetic and thermodynamic study of the reactions of CO2(aq) and HCO3(-) with monoethanolamine (MEA) in aqueous solution

The temperature dependence of the reversible reaction between CO(2)(aq) and monoethanolamine (MEA) has been investigated using stopped-flow spectrophotometry by following the pH changes during the reactions with colored acid-base indicators. Multivariate global analysis of both the forward and backward kinetic measurements for the reaction of CO(2)(aq) with MEA yielded the rate and equilibrium constants, including the protonation constant of MEA carbamate, for the temperature range of 15-45 °C. Analysis of the rate and equilibrium constants in terms of the Arrhenius, Eyring, and van't Hoff relationships gave the relevant thermodynamic parameters. In addition, the rate and equilibrium constants for the slow, reversible reaction of bicarbonate with MEA are reported at 25.0 °C. At high pH, reactions of the amine with CO(2) and with bicarbonate are significant.     

Spectrophotometric studies on ion-pair extraction equilibria of the iron(ii) and iron(III) complexes with 4-(2-pyridylazo)resorcinol

The ion-pair extraction equilibria of the iron(II) and iron(III) chelates of 4-(2-pyridylazo)resorcinol (PAR, H(2)L) are described. The anionic chelates were extracted into chloroform with benzyldimethyltetradecylammonium chloride (QC1) as counter-ion. The extraction constants were estimated to be K(ex1)(Fe(II)) = [Q{Fe(II)(HL)L}](0)/[Q(+)][{Fe(II)(HL)L}(-)] = 10(8.59 +/- 0.11), K(ex2)(Fe(II)) = [Q(2){Fe(II)L(2)}](o)/ [Q(+)](2)[{Fe(II)L(2)}(2-)] = 10(12.17 +/- 0.10) and K(ex1)(Fe(III)) = [Q{Fe((III))L(2)}](o)/(Q(+)][{Fe(III)L(2)}(-)] = 10(6.78 +/- 0.15) at I = 0.10 and 20 degrees , where [ ](o) is concentration in the chloroform phase. Aggregation of Q{Fe(III)L(2)} in chloroform was observed and the dimerization constant (K(d) = [Q(2){Fe(III)L(2)}(2)](o)/[Q{Fe(III)L(2)}](o)(2)) was evaluated as log K(d) = 4.3 +/- 0.3 at 20 degrees . The neutral chelates of {Fe(II)(HL)(2)} and {Fe(III)(HL)L}, and the ion-pair of the cationic chelate, {Fe(III)(HL)(2)}ClO(4), were also extracted into chloroform or nitrobenzene. The relationship between the forms and extraction properties of the iron(II) and iron(III) PAR chelates are discussed in connection with those of the nickel(II) and cobalt(III) complexes. Correlation between the extraction equilibrium data and the elution behaviour of some PAR chelates in ion-pair reversed-phase partition chromatography is also discussed.