Inorganic Reaction Mechanisms (INORG REACT MECH )

Description

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.

  • Impact factor
    0.14
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    Impact factor
  • 5-year impact
    0.28
  • Cited half-life
    0.00
  • Immediacy index
    0.00
  • Eigenfactor
    0.00
  • Article influence
    0.07
  • Website
    Inorganic Reaction Mechanisms website
  • Other titles
    Inorganic reaction mechanisms (Philadelphia, Pa.: Online)
  • ISSN
    1028-6624
  • OCLC
    49941632
  • Material type
    Document, Periodical, Internet resource
  • Document type
    Internet Resource, Computer File, Journal / Magazine / Newspaper

Publications in this journal

  • Inorganic Reaction Mechanisms 01/2012; 37:147-160.
  • 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: 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 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 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: N -bromosuccinimide oxidation of manganate(VI) was studied spectrophotometrically. The reaction showed first order kinetics in [ MnO 4 2 m ] and an apparent less than unit order dependence in [NBS] and rate of reaction decreases with increase in [alkali]. Initial addition of products had no significant effect on the rate of the reaction. The effect of ionic strength and dielectric constant of the reaction medium have been investigated. The results suggest that the reaction proceeds via formation of a complex between active species of oxidant and MnO 4 2 m , which subsequently decomposes in a rate determining step followed by a fast step to yield the products. A mechanism involving the HOBr as the reactive species of the oxidant has been proposed. The reaction constants involved in the mechanism have been computed. There is a good agreement between the observed and calculated rate constants under different experimental conditions. The activation parameters were calculated with respect to the slow step of the proposed mechanism.
    Inorganic Reaction Mechanisms 01/2002; 3(3):213-220.
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    ABSTRACT: The cleavage of the RNA dimers GpA and ApUp is promoted by the inert cobalt(III) complex [Co(tren)(OH 2 )(OH)] 2+ (tren= N , N -bis(2-aminoethyl)ethane-1,2-diamine) the reactions being followed spectrophotometrically, with rate enhancements comparable to those observed for that complex reacting with the model phosphodiester bis( p -nitrophenyl)phosphate. Likewise, the labile [Cu(tach)(OH 2 )(OH)] + complex (tach=cyclohexane-1,3,5-triamine) promotes cleavage of the RNA dimer ApA and trimer ApCpC, observed using electrospray ionization mass spectrometry (ESIMS). Mixtures of ApCpC or ApA and the copper complex prepared at room temperature and examined immediately exhibit peaks assigned to the phosphodiesters and their copper complexes. After heating at elevated temperature for several hours, the ESIMS show clear evidence of cleavage, with peaks due to the parent phosphodiester and their initial complexes absent. While the metal complex promotes the reaction, cyclic phosphodiester intermediates observed also support a trans-esterification cleavage mechanism with a key role for the 2'-OH group on the ribose unit as well as promotion of reaction by metal ion complexation.
    Inorganic Reaction Mechanisms 01/2002; 4(3-4):169-186.
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    ABSTRACT: Chromic acid oxidation of d (+)-xylose in water and in presence of surfactants has an induction period followed by autoacceleration. The kinetics and mechanism of the induction period have been studied spectrophotometrically in both media. Due to precipitate formation, the effect of cetyltrimethylammonium bromide (CTAB, cationic) cannot be studied whereas the oxidation rate increased with increase in sodium dodecyl sulphate (SDS, an-ionic) and octylphenoxypolyethoxy ethanol (TX-100, nonionic) concentration. Reaction is routed through the same mechanism as shown by the kinetic study in the absence and presence of surfactants. Micellar catalysis has been traced to partitioning of the chromic acid species and xylose between the aqueous and micellar pseudo-phases. Rate enhancement in SDS micelles is decreased by ammonium, lithium and sodium ions. Micellar binding/association constants and activation parameters were evaluated and discussed. A mechanism consistent with the results is proposed.
    Inorganic Reaction Mechanisms 01/2002; 3(4):255-266.
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    ABSTRACT: The Lewis bases triphenyl phosphine and triethyl phosphite (L) displace C 60 from ( m 2 -C 60 )W(CO) 5 to produce the complexes ( m 1 -L)W(CO) 5 . These displacement reactions were studied under conditions where the concentrations of C 60 and L were at least 50 times the concentration of ( m 2 -C 60 )W(CO) 5 . The reactions in various solvents were first order with respect to ( m 2 -C 60 )W(CO) 5 . The pseudo first order rate constant values were independent of the concentration and of the nature of L but dependent on the coordinating ability of the solvent under conditions where [C 60 ]/[L] , 0. Under conditions where 0 h [C 60 ]/[L] h 1, the pseudo first order rate constant values decrease as the values of [C 60 ]/[L] increase. Two limiting cases of an interchange displacement of C 60 from ( m 2 -C 60 )W(CO) 5 , whose relative contributions to the overall mechanism depend on the nature of the solvent, are proposed to be a solvent-assisted C 60 -W(CO) 5 bond displacement and a dissociative displacement. The first step of the associative displacement pathway is a solvent-assisted dissociation of C 60 from ( m 2 -C 60 )W(CO) 5 producing the intermediate species (solv)W(CO) 5 , (solv=solvent), whereas the 16 electron unsaturated species W(CO) 5 is produced in the dissociative displacement pathway.
    Inorganic Reaction Mechanisms 01/2002; 4(1-2):49-56.
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    ABSTRACT: Reactions of methylating agents, MeI and Me 3 OBF 4 , with trans -Ir(CO)(Cl)(TPPTS) 2 (TPPTS=P( m -C 6 H 4 SO 3 Na) 3 ) are examined in H 2 O and DMSO. Three products are observed with MeI in water, Ir(CO)(Cl)(I)(Me)(TPPTS) 2 , Ir(CO)(Cl)(Me)(H 2 O)(TPPTS) 2 + and Ir(CO)(I)(Me)(H 2 O)(TPPTS) 2 + ; reactions in the presence of excess Cl m and I m form Ir(CO)(Cl) 2 (Me)(TPPTS) 2 and Ir(CO)(I) 2 (Me)(TPPTS) 2 , respectively. Reaction of trimethyloxonium + with trans -Ir(CO)(CI)(TPPTS) 2 produced only Ir(CO)(Cl)(Me)(H 2 O)(TPPTS) 2 + . None of the methyl compounds underwent hydrolysis or carbonylation.
    Inorganic Reaction Mechanisms 01/2002; 3(4):249-254.