Inorganic Reaction Mechanisms (INORG REACT MECH )


Inorganic Reaction Mechanisms serves the important field of reactions and mechanisms of inorganic systems in solution as the primary specialist international journal in this field. In dealing widely with inorganic reactions in solution, the journal will accept papers pertaining to the areas of coordination chemistry, organometallitic chemistry, main group chemistry and bioinorganic chemistry. It will publish original papers reporting the results of original significant studies in the general area of kinetics and mechanisms of inorganic reactions in solution, and also of studies designed to define reaction pathways or mechanisms via detection and characterization of intermediates by spectroscopic or structural means. Papers dealing with advances in the determination of or processing of data pertaining to mechanistic studies will also be welcomed.

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Publications in this journal

  • Inorganic Reaction Mechanisms 01/2008;
  • Inorganic Reaction Mechanisms 01/2007; 6:169-183.
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    ABSTRACT: Kinetic Studies of the substitution reaction of Ph3SnL1 {L1 = 2-(2,6-dichlorophenyl)aminophenyl acetate} with iodine were carried out in CH2Cl2 using temp. controlled UV-Visible spectroscopy. The reaction for the cleavage of phenyl-Sn bond shows a 1st order dependence on both reactants. Activation parameters are reported and on the basis of low values of activation enthalpy and entropy, the presence of an intermediate π complex is suggested for the reaction. The associative mechanism plays a major part in such reactions.
    Inorganic Reaction Mechanisms 01/2006; 6(1):49-58.
  • Inorganic Reaction Mechanisms 01/2006;
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    ABSTRACT: The kinetics of the interaction of glutathione (reduced) (GSH) with [Pt(en)(H2O)2](ClO4)2 and [Pt(dmen)(H2O)2](ClO4)2 (en = ethylenediamine, dmen = N,N′-dimethylethylenediamine) have been studied spectrophotometrically as a function of [substrate complex], [glutathione] and temperature at a particular pH (4.0). The reaction was found to proceed via rapid outersphere association complex formation followed by two slow consecutive steps. The first step involves the transformation of the outersphere complex into the innersphere complex containing Pt-S bond, while the second step involves chelation when the second aqua ligand is displaced. The association equlibrium constant (KE) and the two rate constants k1 and k2 have been evaluated. Activation parameters for both the steps have been calculated using Eyring equation. The low enthalpy of activation and large negative values of entropy of activation indicate an associative mode of activation for both steps.
    Inorganic Reaction Mechanisms 03/2003;
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    ABSTRACT: Sodium nitroprusside (SNP) is a well-known vasodilator, which activates the cytosolic isozyme guanylate cyclase. It is quite stable by itself in aqueous solution and in the dark, but produces nitric oxide spontaneously under the appropriate reducing conditions. Both the neutral nitric oxide (NO) and the nitroxyl anion (NO m ) can be produced from SNP depending on the condition employed. NO release is favored at lower pH and cysteine concentration while NO m formation is more likely to occur at higher pH (>7) and cysteine concentration. NO was measured by electrochemical method and the chemical detection of NH 2 OH and NO 2 m are evidences of NO m formation. The mechanism of the reaction was found to be very complicated and involved three clear stages. NO and NO m are postulated to form in the first and third stages, respectively. All three stages showed cysteine dependence and were also affected by the pH of the solution. The first two stages resembled stepwise reversible two-electron reduction of NO + to NO m and are similar in rates. However the third stage is the slowest irreversible and rate-determining substitution of NO m by cysteine in the reduced nitroprusside ion. Increased absorption occurs between 250 and 500 u nm for the first two stages with absorption maxima at about 340 u nm for the first two stages which signals NO reduction in nitroprusside. A decrease in absorption in the same region, which signal loss of NO m was observed for the third stage of the reaction sequence. Cyanide release occurs in the first stage and the addition of NaCN significantly retards the reaction rate proving the reversible loss of CN m from the nitroprusside ion. Transition metal ions are known to catalyze the decay of nitrosocompounds and addition of Cu 2+ to reaction solutions showed significant catalysis and was especially pronounced in the final stage.
    Inorganic Reaction Mechanisms 01/2002; 3(3):181-195.
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    ABSTRACT: The rates and steric course for the Me 2 SO substitution reactions for cis - and trans -[Co(en) 2 (OSMe 2 )(N 3 )] 2+ in solvent Me 2 SO have been investigated by 1 H NMR and Vis./UV spectroscopy. Isomerisation, racemisation, solvent exchange and NH scrambling experiments for selectively-deuterated complexes are reported which provide a wider picture on the octahedral substitution process and the nature of the intermediates than previously possible. The results show that the traditional accounts appearing in standard texts are in need of revamping.
    Inorganic Reaction Mechanisms 01/2002; 4:141-157.
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    ABSTRACT: New complexes of Co(II), Ni(II) and Cu(II) with di(3-chloro-4-methylphenyl) carbazone having the general formula [M(DCMPC) 2 ] [where M=Co(II), Ni(II) or Cu(II); DCMPC=di(3-chloro-4-methylphenyl)carbazone] have been synthesized and characterized by elemental analyses, magnetic moment measurements, Uv-Vis., IR, EPR and thermal studies. The DCMPC behaves as a bidentate monoanionic ligand coordinating through the ketonic oxygen and azo nitrogen. The interpretation, mathematical analyses of the thermoanalytical data (TG and DTA) and evaluation of kinetic parameters are presented in this communication. The energy of activation for the two clear-cut steps of decomposition for all the complexes are compared by employing the Freeman-Carroll equation, the integration method using the Coats-Redfern equation and the approximation method using the Horowitz-Metzger equation. The Coats-Redfern equation was extended to evaluate other kinetic parameters such as pre-exponential factor and entropy of activation.
    Inorganic Reaction Mechanisms 01/2002; 4:89-93.
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    ABSTRACT: Exchange reactions of gold(I) thiomalate (AuStm) n with two diselenides (RSe-SeR), selenocystine and selenocystamine have been studied in D 2 O by 13 C NMR spectroscopy. Upon interaction of diselenides with (AuStm) n , the Se-Se bond is broken, resulting in the formation of RSe-Stm and (AuSeR) n species. RSe-Stm on further decomposition leads to the formation of thiomalic disufide (Stm) 2 . The second order rate constant was determined for the decomposition of RSe-Stm species and is found to be 3.21 2 10 m 4 l mol m 1 s m 1 . The intensity of thiomalic disulfide resonances increases, while the intensity of RSe-Stm resonances decreases with time. The end result of both reactions is the formation of (Stm) 2 and the deposition of metallic gold and brown ppts. In both cases exchange takes place immediately, however, the overall reaction of (AuStm) n with selenocystamine was faster than with selenocystine.
    Inorganic Reaction Mechanisms 01/2002; 4:95-102.
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    ABSTRACT: Conventional and stopped-flow spectrophotometry was used to study the kinetics of ligand substitution in a number of mono g -diketone salen iron(III) complexes, [Fe(salen)(O 7 O)], by 8-hydroxyquinoline (=HO 7 N) in alcohol media (O 7 O m =anion of the g -diketones pentane-2,4-dione, 2,6-dimethylheptane-3,5-dione, 2,2,6,6-tetramethylheptane-3,5-dione, 1-phenylbutane-1,3-dione, 1,3-diphenylpropane-1,3-dione, and 1-(2-thienyl)-4,4,4-trifluorobutane-1,3-dione; salen=anion of N , N '-disalicylideneethylenediamine). As shown by spectrophotometry and conductometry, the solutions of complexes [Fe(salen)(O 7 O)] in alcohols ROH are subject to solvolytic dissociation, leading to neutral and charged solvento species [Fe(salen)S 2 ] (S=RO m and ROH, respectively). The dissociation constants K D for the systems [Fe(salen)(O 7 O)]/ROH, as determined by concentration-jump experiments as well as by dilution experiments, range from 3 2 10 m 5 M to 1 2 10 m 3 M. The reaction of complexes [Fe(salen)(O 7 O)] with HO 7 N in alcohols is biphasic, with first-order rate constant k 1 describing the initial solvolytic dissociation of [Fe(salen)(O 7 O)] (solvent assisted D-mechanism) and second-order rate constant k 2 , the consecutive reaction of the solvento species [Fe(salen)S 2 ] with HO 7 N to form [Fe(salen)(O 7 N)]. Depending on the nature of the coordinated g -diketone and solvent ROH, k 1 ranges from 0.12 to 31 s m 1 and k 2 from 1 2 10 3 to 26 2 10 3 M m 1 s m 1 at 298 K. Both the initial solvolysis step and the consecutive anation step involve a change in the coordination of the Salen ligand from non-planar to planar and vice versa .
    Inorganic Reaction Mechanisms 01/2002; 3(4):221-232.
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    ABSTRACT: The reaction of dichloro-{1-benzyl-2-(arylazo)imidazole}palladium(II), [Pd(R'aaiBz)Cl 2 ], where R'aaiBz= p -R'-C 6 H 4 -N=N-C 3 H 2 N 2 -1-CH 2 -C 6 H 5 ; R'=H (1), Me (2), Cl (3), with pyridine bases [RPy: R=H (a), 4-Me (b), 4-Cl (c), 2-Me (d), 2,6-Me 2 (e), 2,4,6-Me 3 (f)] has been studied spectrophotometrically in MeCN at 468 nm. The products (4) have been isolated and characterised as trans -Pd(RPy) 2 Cl 2 . The kinetics of the nucleophilic substitution has been examined under pseudo-first-order conditions at 298 K. The single phase reaction step has been observed for the bases HPy (a), 4-MePy (b) and 4-ClPy (c) and follows the rate law, rate= k [RPy] 2 [Pd(R'aaiBz)Cl 2 ]. The bases, 2-MePy (d), 2,6-Me 2 Py (e) and 2,4,6-Me 3 Py (f) exhibit bi-phasic reaction: rate-1= k ' [RPy][Pd(R'aaiBz)Cl 2 ] and rate-2= k " [RPy][Pd(R'aaiBz)Cl 2 ]. The rate data support nucleophilic association path. External addition of Cl m (LiCl) suppresses the rate, that follows the order; k / k '/ k " (3) > k / k '/ k " (1) > k / k '/ k " (2). The k 's are linearly related to Hammett † constants. The 2-MePy, 2,6-Me 2 Py and 2,4,6-Me 3 Py remarkably reduce the rate compared with 4-substituted pyridine bases. This is attributed to steric effect that destabilises the transition state. The rate decreases with increasing steric crowding at the ortho -position and follows the order: (d)>(f)>(e). The 4-substituted pyridine controls the rate via inductive effect and follows the order: (b)>(a)>(c).
    Inorganic Reaction Mechanisms 01/2002; 4:57-65.
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    ABSTRACT: The kinetics of the oxidation of sulfamethoxazole (SMZ) by permanganate in aqueous alkaline medium at constant ionic strength of 0.41 mol dm m 3 was studied spectrophotometrically. The reaction is of first order in [permanganate ion] and has apparent less than unit order in both [SMZ] and [alkali]. Addition of products have no significant effect on the reaction rate. However, increasing ionic strength and decreasing dielectric constant of the medium increase the rate. The oxidation in alkaline medium has been shown to proceed via an alkali-permanganate species, which forms a complex with SMZ. The latter decomposes slowly, followed by a fast reaction between a free radical of SMZ and another molecule of permanganate to give the products. The reaction constants involved in the mechanism were evaluated and there is a good agreement between observed rate constants and the calculated rate constants. The activation parameters were computed with respect to the slow step of the proposed mechanism.
    Inorganic Reaction Mechanisms 01/2002; 3(4):239-247.
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    ABSTRACT: The effect of nonionic Triton X-100 (TX-100) micelles on the pseudo-first order rate constants ( k ƒ ) for the oxidation of EDTA by chromic acid has been studied at different perchloric acid concentrations. The micellar-mediated reaction was independent of chromic acid concentration whereas first- and complex-order dependence on [EDTA] and [HClO 4 ], respectively, were observed. Increase in the total concentration of TX-100 from 0.0 to 60.0 2 10 m 3 mol dm m 3 caused the k ƒ to increase by nearly 4-fold at constant temperature and [HClO 4 ]. The observed catalytic effect has been explained on the basis of pseudo-phase kinetic and Piszkiewicz models. The higher rate of EDTA oxidation in the micellar pseudo-phase is attributed to association of the reactants with the nonionic micellar head groups through hydrogen bonding. A mechanism is proposed in accordance with the experimental results obtained.
    Inorganic Reaction Mechanisms 01/2002; 4:187-196.
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    ABSTRACT: Acid-catalysed hydrolysis kinetics were studied for 14 cobalt(III) carbonato complexes involving the title five at oxonium ion concentration of 0.01-1.0 M, ionic strength of 2.0 (NaClO 4 ) and 15-45°C (M=mol dm m 3 ). Preprotonation constant, about 1 M m 1 , was estimated from a non-linear acidity dependence of an experimental rate constant for the ring-opening of the didentate hydrogencarbonato intermediate. Acidity constant, 0.003-0.7 M, and basicity constant, 0.1-0.9 M m 1 , of the ring-opened aquahydrogencarbonato intermediate were estimated from an acidity dependence of an experimental rate constant for the decarboxylation. Concerning the widely ranging ring-opening rate constants (0.05-126 s m 1 at 25°C), we demonstrate labilizing effects of a reduced charge and of small tetrakis(amine) ligand, correlating with a high activation entropy, as well as of the trans five-membered chelate correlating with a low activation energy. The charge effect may be understood by the solvational change during the dissociative activation. Activation parameters of the uniform decarboxylation rate constant (0.2-4 s m 1 at 25°C) from the aquahydrogencarbonato intermediate are higher than those of the decarboxylation from carbonic acid. This may be relevant to a Co-O bond rotation prior to the decarboxylation. The isometric structures of carbonato(ethylenediamine)(glycinato)cobalt(III) are studied by X-ray crystallography.
    Inorganic Reaction Mechanisms 01/2002; 4:221-232.
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    ABSTRACT: The synthesis and properties of [(NH3)(5) CoOSO2Cl](ClO4 ) (2) are described. This complex is one of the most reactive cobalt(III) species ever isolated (t(1/2) 10 s; 25degreesC; 0.1 M HClO4). In water it yields [(NH3)(5-) CoOSO3](+) , [(NH3)(5) CoOH2](3+) and [(NH3)(5) CoCl](2+) . The first two of these products come from the expected direct S-Cl and Co-O cleavages. The chloro complex arises via intramolecular linkage isomerisation to the transient [(NH3)(5)Co-ClSO3](2+) species which then cleaves the S-Cl bond. Considerable attention is given to the characterisation of the Co-O3SCl species, including reaction in O-17-H2O where the NMR spectra confirm Co-(17) OSO3 , Co-(OH2)-O-17 and free (OSO32-)-O-17 products. The reactions have been studied also in aqueous base, 0.1 M HClO4 and Me2SO where the same reactions are observed but in quite different proportions. In liquid ammonia, with or without added NH4+ , no O-bonded sulphamate complex [(NH3)(5)CoOSO2NH2](2+) arising from direct S-Cl cleavage is observed. The linkage isomerisation pathway is more pronounced in the absence of base, and this is usual. Mechanisms are discussed in relation to the analogous Co(III)-FSO3- chemistry and to the hydrolysis reactions of the free FSO3- and ClSO3- anions. The most remarkable result is that the ClSO3- ion (and likely FSO3- as well) is substantially deactivated on coordination to Co(III), and such protection is most unusual and no doubt the reason for a successful isolation of the complex of a ligand which hydrolyses in millisec. It can be recovered substantially intact by rapid recrystallisation from water.
    Inorganic Reaction Mechanisms 01/2002;
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    ABSTRACT: The synthesis of the putative trans -[Co(en)2(py)Cl]2+ complex, isolated as various salts, is reported. New or revised procedures are given for precursor complexes, some of which were known previously, and 2D NMR studies which permit the unambiguous assignment of the NH resonances for all the trans ions. NMR characterisation of a synthetic precursor, the double salt trans -[(NO2)(en)2Co(OH)···H···(OH)Co(en)2(NO2)]3+, which entails the symmetric bridging H3O2 - ion in the solid state ( X -ray structure), provides evidence of a kinetic role for the H3O2 - bridge which must persist at low levels in solution. Reliable NMR techniques for assigning the NH protons are discussed. The synthesis and a reliable optical resolution of the well known cis-[Co(en)2 (py)Cl]2+ complex are also reported, along with the syntheses of trans -, rac-cis and Λ- cis -[Co(en)2 (py)OH2]3+ derivatives, all isolated for the first time. ORD and CD data are reported for all the resolved ions, and absolute configurations have been determined through chemical correlations.
    Inorganic Reaction Mechanisms 01/2002; 4(3-4):111-124.
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    ABSTRACT: The kinetics of the reaction of [Pt(digly)(H 2 O)] (where H 2 digly=glycylglycine) with imidazole, pyrazole and triazole were studied at 25°C in aqueous medium by UV-Vis. spectroscopy at I =0.1 mol dm m 3 in the range of pH=5.05-9.00. The entry of the azole bases by the substitution of aqua ligand was revealed. All the products have been characterized through CHN analysis, IR and 1 H NMR spectra. The pH variation data were fitted by a computer fit program and the reactivity of the different azole base species towards the Pt(II) substrate ascertained.
    Inorganic Reaction Mechanisms 01/2002; 4:159-167.