Mechanisms of substitution reactions on cyclometallated platinum(IV) complexes: "Quasi-labile" systems

The substitution reactions of SMe2 by phosphines (PMePh2, PEtPh2, PPh3, P(4-MeC6H4)(3), P(3-MeC6H4)(3), PCy3) on Pt-IV complexes having a cyclometalated imine ligand, two methyl groups in a cis-geometrical arrangement, a halogen, and a dimethyl sulfide as ligands, [Pt(CN)(CH3)(2)(X)(SMe2)], have been studied as a function of temperature, solvent, and electronic and steric characteristics of the phosphines and the X and CN ligands. In all cases, a limiting dissociative mechanism has been found, where the dissociation of the SMe2 ligand corresponds to the rate-determining step. The pentacoordinated species formed behaves as a true pentacoordinated Pt-IV compound in a steady-state concentration, given the solvent independence of the rate constant. The X-ray crystal structures of two of the dimethyl sulfide complexes and a derivative of the pentacoordinate intermediate have been determined. Differences in the individual rate constants for the entrance of the phosphine ligand can only be estimated as reactivity ratios. In all cases an effect of the phosphine size is detected, indicating that an associative step takes place from the pentacoordinated intermediate. The nature of the (CN) imine and X ligands produces differences in the dimethyl sulfide dissociation reactions rates, which can be quantified by the corresponding DeltaS double dagger values (72, 64, 48, 31, and 78 J K-1 mol(-1) for CN/X being C6H4CHNCH2C6H5/Br, C6H4CHNCH2-(2,4,6-(CH3)(3))C6H2/Br, C6H4CHNCH2C6H5/Cl, C6Cl4CHNCH2C6H5/Cl, and C6W4CH2NCHC6H5/ Pr, respectively). As a whole, the donor character of the coordinated C-aromatic and X atoms have the greatest influence on the dissociativeness of the rate-determining step.

Opposite roles of O-2 in NO- and N2O-carbon reactions: An ab initio study

Previous experimental studies showed that the presence of O-2 greatly enhances NO-carbon reaction while it depresses N2O-carbon reaction on carbon surfaces. A popular explanation for the rate increase is that the addition of O-2 results in a large number of reactive carbon-oxygen complexes, and decomposition of these complexes produces many more active sites. The explanation for the latter is that excess O-2 simply blocks the active sites, thus reducing the rate of N2O-carbon reaction. The contradiction is that O-2 can also occupy active sites in NO-carbon reaction and produce active sites in N2O-carbon reduction. By using ab initio calculation, we find that the opposite roles of O-2 are caused by the different manners of N2O and NO adsorption on the carbon surface. In the presence of excess O-2, most Of the active sites are occupied by oxygen groups. In the competition for the remaining active sites, NO is more likely to chemisorb in the form of NO2 and NO chemisorption is mon thermodynamically favorable than O-2 chemisorption. By contrast, the presence of excess O-2 makes N2O chemisorption much less thermally stable either on the consecutive edge sites or edge sites isolated by semiquinone oxygen. A detailed analysis and discussion of the reaction mechanism of N-2 formation from NO- and N2O-carbon reaction in the presence of O-2 is presented in this paper.

Employee reactions to behavioural control under conditions of stress: the moderating role of self-efficacy

Extensive research conducted in the occupational stress literature has failed to provide convincing support for the stress-buffering effects of work control on employee adjustment. Drawing on research conducted in the laboratory context, it was proposed that the stress-buffering effects of work control on employee adjustment would be more marked at high, rather than low, levels of self-efficacy. In a sample of 100 customer service representatives, a significant three-way interaction among role conflict, work control and self-efficacy (measured at Time 1) was observed on (low) depersonalization (measured at Time 2). Consistent with expectations, work control reduced the negative effects of work stress on this outcome measure only for employees who perceived high levels of self-efficacy at work. In addition, there was evidence to suggest that self-efficacy moderated the main effects of work control on job satisfaction and somatic health. These findings are discussed hi terms of their theoretical contribution to the job strain model, and also in relation to workplace interventions designed to improve levels of employee adjustment.

Photochemical Reactions of fac-[Mn(CO)(3)(phen)imidazole](+): Evidence for Long-Lived Radical Species Intermediates

The electronic absorption spectrum of fac[Mn(CO)(3)(phen)imH](+), fac-1 in CH(2)Cl(2) is characterized by a strong absorption band at 378 nm (epsilon(max) = 3200 mol(-1) L cm(-1)). On the basis of quantum mechanical calculations, the visible absorption band has been assigned to ligand-to-ligand charge-transfer (LLCT, im -> phen) and metal-to-ligand charge-transfer (MLCT, Mn -> phen) charge transfer transition. When fac-1 in CH(2)Cl(2) is irradiated with 350 nm continuous light, the absorption features are gradually shifted to represent those of the meridional complex mer-[Mn(CO)(3)(phen)imH](+), mer-1 (lambda(max) = 556 nm). The net photoreaction under these conditions is a photoisomerization, although, the presence of the long-lived radical species was also detected by (1)H NMR and FTIR spectroscopy. 355 nm continuous photolysis of fac-1 in CH(3)CN solution also gives the long-lived intermediate which is readly trapped by metylviologen (MV(2+)) giving rise to the formation of the one-electron reduced methyl viologen (MV(center dot+)). The UV-vis spectra monitored during the slow (45 min) thermal back reaction exhibited isosbestic conversion at 426 nm. On the basis of spectroscopic techniques and quantum mechanical calculations, the role of the radicals produced is analyzed.

Recognition of cyclic, acyclic, exocyclic, and spiro Acetals via structurally diagnostic ion/molecule reactions with the (CH3)(2)N-C+=O acylium ion

Reactions of the model acylium ion (CH3)(2)N-C+=O with acyclic, exocyclic, and Spiro acetals of the general formula (RO)-O-1-(CRR4)-R-3-OR2-upole mass spectrometry. Characteristic intrinsic reactivities were observed for each of these classes of acetals. The two most Characteristic intrinsic reactivities were observed for each of these classes of acetals. The two most common reactions observed were hydride and alkoxy anion [(RO-)-O-1 and (RO-)-O-2] abstraction. Other specific reactions were also observed: (a) a secondary polar [4(+) + 2] cycloaddition for acetals bearing alpha,beta-unsaturated R-3 or R-4 substituents and (b) OH- abstraction for exocyclic and spiro acetals. These structurally diagnostic reactions, in conjunction with others observed previously for cyclic acetals, are shown to reveal the class of the acetal molecule and its ring type and substituents and to permit their recognition and distinction from other classes of isomeric molecules.

Evaluation of the enthalpy of formation, proton affinity, and gas-phase basicity of gamma-butyrolactone and 2-pyrrolidinone by isodesmic reactions

The knowledge of thermochemical parameters such as the enthalpy of formation, gas-phase basicity, and proton affinity may be the key to understanding molecular reactivity. The obtention of these thermochemical parameters by theoretical chemical models may be advantageous when experimental measurements are difficult to accomplish. The development of ab initio composite models represents a major advance in the obtention of these thermochemical parameters,. but these methods do not always lead to accurate values. Aiming at achieving a comparison between the ab initio models and the hybrid models based on the density functional theory (DFT), we have studied gamma-butyrolactone and 2-pyrrolidinone with a goal of obtaining high-quality thermochemical parameters using the composite chemical models G2, G2MP2, MP2, G3, CBS-Q, CBS-4, and CBS-QB3; the DFT methods B3LYP, B3P86, PW91PW91, mPW1PW, and B98; and the basis sets 6-31G(d), 6-31+G(d), 6-31G(d,p), 6-31+G(d,p), 6-31++G(d,p), 6-311G(d), 6-311+G(d), 6-311G(d,p), 6-311+G(d,p), 6-311++G(d,p), aug-cc-pVDZ, and aug-cc-pVTZ. Values obtained for the enthalpies of formation, proton affinity, and gas-phase basicity of the two target molecules were compared to the experimental data reported in the literature. The best results were achieved with the use of DFT models, and the B3LYP method led to the most accurate data.

Niobium to alcohol mol ratio control of the concurring esterification and etherification reactions promoted by NbCl5 and Al2O3 catalysts under microwave irradiation

Alcohols and acids can be switched to produce ethers or esters by varying the alcohol to catalyst mol ratio, in a new etherification and esterification method using NbCl5/Al2O3 catalyst under ""solvent free"" conditions and promoted by MW (microwave) irradiation. A ""two sites"" mechanism for the reaction is proposed, in an attempt to clarify the tendency of the catalyst to be dependent on the alcohol alone during the esterification process. (c) 2008 Elsevier B.V. All rights reserved.

Hydroalumination of Thioacetylenes: A Versatile Generation and Reactions of -Aluminate Sulfides Intermediates

Hydroalumination of thioacetylenes using DIBAL-H and lithium di-(isobutyl)-n-(butyl)-aluminate hydride (Zweifel`s reagent), followed by addition of water, furnished exclusively the (Z)- and (E)-vinyl sulfides, respectively. The regio- and stereochemistry of the intermediates generated, (Z)- and (E)-phenylthio vinyl alanates, were determined by capture with iodine, which afforded the corresponding (E)- and (Z)-1-iodo-1-phenylthio-2-organoyl ethenes. Reactions of the (E)-iodo(thio)ketene acetals with n-BuLi followed by addition of hexanal afforded the (Z)-phenylthio allylic alcohol, while the (Z)-iodo(thio)ketene acetals under similar reactions conditions gave the (E)-phenylthio allylic alcohol exclusively.

A new oxovanadium(IV)-cucurbit[6]uril complex: Properties and potential for confined heterogeneous catalytic oxidation reactions

This work presents a new oxovanadium(IV)-cucurbit[6]uril complex, which combines the catalytic properties of the metal ion with the size-excluding properties of the macrocycle cavity. In this coordination compound, the VO(2-) ions are coordinated to the oxygen atoms located at the rim of the macrocycle in slightly distorted square-pyramidal configurations, which are in fact C(2v) symmetries. This combination results in a size-selective heterogeneous catalyst, which is able to oxidize linear alkanes like n-pentane at room temperature, but not styrene, cyclohexane or z-cyclooctene, which are too big to enter the cucurbit[6]uril cavity. The results presented here contribute to understanding the mechanism of alkane catalytic oxidation by oxovanadium(IV) complexes. (C) 2010 Elsevier Ltd. All rights reserved.

Synthesis of (Z)-tributylstannyl enynes: systematic studies of Sonogashira cross-coupling reactions between (E)-1-iodovinyl-1-tributylstannanes and terminal acetylenes using amines or tetrabutylammonium hydroxide (TBAOH) as activator

Sonogashira cross-coupling reactions involving (E)-iodo vinyl stannanes and terminal acetylenes were carried out in the presence of Pd(PPh(3))(4), Cul and several amines, affording (Z)-tributylstannyl enynes in moderate to good yields (62-91%). Utilizing the catalytic system containing Pd(PPh(3))(4) (5%), Cul (10%), and TBAOH (40% in aqueous media) as activator, better yields (72-91%) and lower reaction times were achieved. (C) 2011 Elsevier Ltd. All rights reserved.

An approach to the synthesis of furanoheliangolides through Diels-Alder reactions

The core structure of the natural sesquiterpene lactones furanoheliangolides, an 11-oxabicyclo[6.2.1]undecane system, was synthesized through a pathway involving two Diels-Alder reactions. (c) 2007 Elsevier Ltd. All rights reserved.

N-methylation of diamino-substituted macrocyclic complexes: Intermolecular reactions

Two N-based isomeric copper(II) complexes of the macrocycle trans-6,13-dimethyl-6,13-bis(dimethylamino)1,4,8,11-tetraazacyclotetradecane (L(3)) have been synthesized and characterised spectroscopically and structurally: alpha-[CuL(3)(OH2)(2)]Cl-2, monoclinic, space group C2/m, a = 12.908(4), b = 12.433(2), c = 7.330(2) Angstrom, beta = 105.87(2)degrees, Z = 2; beta-[CuL(3)(OClO3)(2)]. 2H(2)O, monoclinic, space group P2(1)/c, a = 9.708(3), b = 9.686(3), c = 14.202(4) Angstrom, beta = 106.17(1)degrees, Z = 2. The two isomers exhibit very similar co-ordination spheres but significantly different visible electronic maxima. This difference is attributed to an intramolecular N ... H contact between the pendant dimethylamino group and an adjacent secondary amine H atom.

Differential disease reactions on lucerne genotypes inoculated with Phytophthora medicaginis isolates from lucerne and chickpea

Stem inoculation of clonally propagated lucerne genotypes was used to assess levels of host species and genotype specialisation in Phytophthora medicaginis. A quantitative assessment of pathogenic aggressiveness of 29 P. medicaginis isolates (from lucerne and chickpea) on 9 different clonally propagated lucerne genotypes revealed no significant difference in aggressiveness between isolates from lucerne and those from chickpea on all of the lucerne genotypes. This supported previous studies which showed that P. medicaginis isolates from lucerne and chickpea were indistinguishable using random amplified polymorphic DNA (RAPD) analysis. Analysis of pathogenic aggressiveness towards individual lucerne genotypes revealed, for the first time, specificity of individual P. medicaginis isolates. This has implications for breeding for resistance to P. medicaginis in lucerne, where screening should be done using the widest range of pathogen specificity obtainable.

Macrocycle formation through carbon acid-formaldehyde condensation reactions of bis(propane-1,2-diamine)- and bis (2-methylpropane-1,2-diamine)-copper(II) ions

The reaction of the bis(1,2-diamine) copper(II) complexes of racemic propane-1,2-diamine (pn) and 2-methylpropane-1,2-diamine (dmen) with formaldehyde and nitroethane in methanol under basic conditions yields minor macrocyclic condensation products in addition to the major acyclic products. Where C-pendant methyl groups on the pair of coordinated diamines are in cis dispositions, the first -NH-CH2-C(CH3)(NO2)-CH2-NH- ring formation occurs at amine pairs distant from these C-methyl substituents, and further reaction to yield a macrocycle is not observed. However, where the C-methyl substituents are in trans dispositions, the chemistry proceeds to yield the macrocycle. Commencing with pn, trans-(6,13-diammonio-2,6,9,13-tetramethyl-1,4,7,10-tetraazacyclotetradecane)copper(II) perchlorate formed and crystallized in the space group P2(1)/n, with a 9.782(2), b 9.2794(6), c 17.017(4) Angstrom, beta 103.24(1)degrees. The copper ion is found in a square-planar environment, with the two methyl groups of the pn residues and the pairs of introduced pendant groups all in trans arrangements.