UNIMOLECULAR DISSOCIATION REACTIONS OF DOUBLY-CHARGED IONS [C12H12N2O](2+) AND [C12H12N2S](2+) IN GAS-PHASE

The unimolecular dissociation reactions of doubly charged ions were reported, which resulted from a tandem mass spectrometer and a reversed geometry double focusing mass spectrometer by electron impact, Mass analyzed ion kinetic energy spectrometry (MIKES) was used to obtain the kinetic energy releases in charge separation reactions of doubly charged ions, The intercharge distances between the two charges at transition states can be calculated from the kinetic energy releases, Transition structures of unimolecular dissociation reactions were infered from MIKES and MS/MS.

GAS-PHASE ACETYLATION OF C-60 AND C-70 BY ION/MOLECULE REACTIONS

Gas phase reactions of C-60 and C-70 with the ion system of acetone under chemical ionization conditions have been studied. C-60 and C-70 can react with acetyl and oxonium ions, which come from self-chemical ionization of acetone, to form adduct ions. In addition, C-60 and C-70 can accept protons to produce protonated ions. C-70 is more active in the above reactions than C-60 because of its stronger gas-phase basicity. A sigma-bond between C-60 and an acyl carbon atom can be formed to produce stable acetylated C-60 ions. The above results may be relevant to the acetylation reactions of C-60 in the condensed phase.

Gas-phase Ion-molecular Reactions of C-60 and C-70 with Acetone and Quantum Chemistry Study

Gas-phase ion-molecular reactions of C-60 and C-70 with the ion system of acetone have been studied in this paper. The ions of protoned and acetylized C-60 and C-70 were formed by the reactions of C-60 and C-70 with some ions which existed in the ion system when mass spectrometer worked on chemical ionization conditions. The reactivity of C-70 is greater than that of C-60. Results of quantum chemical calculation for the adduct ions showed a sigma bond between the acyl carbon atom and C-60 may be Formed. These results will provide some valuable informations on the condense-phase acetylization of C-60.

DIRECT ELECTROCHEMICAL REACTIONS OF CYTOCHROME-C AT IODIDE-MODIFIED ELECTRODES

Quasi-reversible and direct electron transfer was observed between an iodide-modified Au electrode and cytochrome c, as well as between cytochrome c in an iodide-containing solution and a bare Au electrode. The results suggest that an electrostatic intera

STUDIES OF ELECTROCHEMICAL CATALYTIC REDUCTION REACTIONS OF TETRAPHENYLPORPHINATOCOBALT 1,2-DIBROMOETHANE AND 1,2-DICHLOROETHANE SYSTEMS IN NONAQUEOUS MEDIA

Electrochemical catalytic reactions of tetraphenylporphinatocobalt were studied in DMF and EtCl2 solutions in the presence of 1,2-dibromoethane and 1, 2-dichloroethane utilizing cyclic voltammetry, thin-layer electrochemistry, in situ UV-visible spectroel

APPLICATION OF AN ULTRAMICROELECTRODE IN HOMOGENEOUS CATALYTIC REACTIONS .4. ELECTROCATALYTIC REDUCTION OF ORGANOHALIDES BY METALLOPORPHYRIN AT ULTRAMICROELECTRODE

The electrocatalytic reduction of 1,2-dibromoethane and tetrabromoethane with CoTPP in DMF solutions containing 0.1 M TBAP was investigated at a Pt ultramicroelectrode. The experimental results indicated that CoTPP obviously exhibited catalytic activity for 1,2-dibromoethane and tetrabromoethane. The rate constants of 1,2-dibromoethane and tetrabromoethane in this system were calculated to be 0.14 x 10(3) and 0.5 x 10(2) M-1 S-1, respectively. The reaction mechanism of 1,2-dibromoethane and tetrabromoethane reduction electrocatalysed by CoTPP in 0.1 M TBAP DMF solution is discussed.

STUDIES ON THE REACTIONS OF TRANSITION-METAL HYDRIDES WITH HETEROCUMULENES .6. REACTION OF CP2ZR(H)CL WITH RNCS (R=C6H5, 2-C10H7, C-C6H11 AND N-C4H9)

The novel NS-containing zirconacycle complexes Cp2ZrCl[SC(H)NR] (1a, R = C6H5; 1b, R = 2-C10H7; 1c, R= C-C6H11; 1d; R = n-C4H9) were obtained by insertion reactions of Cp2Zr(H)Cl with RNCS. 1(a-d) could react further with Cp2Zr(H)Cl to yield a sulphur-bridging compleX (Cp2ZrCl)2S (2) and a Schiff base RN=CH2. The crystal structure of la has been determined by X-ray analysis.

APPLICATION OF ULTRAMICROELECTRODES IN STUDIES OF HOMOGENEOUS CATALYTIC REACTIONS .2. A THEORY OF QUASI-1ST AND 2ND-ORDER HOMOGENEOUS CATALYTIC REACTIONS

The analytical expressions of quasi-first and second order homogeneous catalytic reactions with different diffusion coefficients at ultramicrodisk electrodes under steady state conditions are obtained by using the reaction layer concept. The method of treatment is simple and its physical meaning is clear. The relationship between the diffusion layer, reaction layer, the electrode dimension and the kinetic rate constant at an ultramicroelectrode is discussed and the factor effect on the reaction order is described. The order of a catalytic reaction at an ultramicroelectrode under steady state conditions is related not only to C(Z)*/C(O)* but also to the kinetic rate constant and the dimension of the ultramicroelectrode; thus the order of reaction can be controlled by the dimension of the ultramicroelectrode. The steady state voltammetry of the ultramicroelectrode is one of the most simple methods available to study the kinetics of fast catalytic reactions.

APPLICATION OF ULTRAMICROELECTRODES IN STUDIES OF HOMOGENEOUS CATALYTIC REACTIONS .3. THE CONDITION FOR QUASI-1ST AND 2ND-ORDER HOMOGENEOUS CATALYTIC REACTIONS AT ULTRAMICRODISK ELECTRODES IN THE STEADY-STATE

The conditions for quasi-first and second order homogeneous catalytic reactions and their variation with each other at an ultramicrodisk electrode in the steady state are discussed in this paper. The order of reaction can be controlled by changing the dimension of the ultramicroelectrode: the second order reaction can be changed to quasi-first by decreasing the dimension of the ultramicroelectrode. An example of this is given. The main factor effect on the reaction order is the dimension of the ultramicroelectrode. The K4Fe(CN)6-aminopyrine system is selected to confirm the theory, the experiments showing that the system is a second order reaction at a 432 mum microelectrode, and a quasi-first order reaction at a 19 mum ultramicroelectrode. The kinetic constant of the system can be determined by applying the previous theory of homogeneous catalytic reaction.

DIELS-ALDER REACTIONS CATALYZED BY LANTHANIDE CHLORIDES

Lanthanide chlorides have been found to catalyze the Diels-Alder synthesis of 2-butoxy-3, 4-dihydro-2H-pyran and several norbornene derivatives under mild conditions. In particular, the heavier lanthanide chlorides are very active catalysts for some (4 + 2) cycloaddition reactions. The catalyst activities and selectivities generally increase with increasing atomic number of the rare earth elements.

稀土氯化物催化的Diels—Alder反应

本文提出以稀土氯化物作催化剂,催化等摩尔比的丙烯醛和乙烯基丁醚进行环加成反应,生成2-丁氧基-3,4-二氢-2H-吡喃。实验表明,环加成产物是不稳定的中间物,它可以进一步开环聚合构成一个催化的连串反应。找到了稳定中间物的反应条件,以90—95％产率得到环加成产物。

Addition reactions of nitrones on the reconstructed C(100)-2 x 1 surfaces

In this paper, the reactions of nitrone, N-methyl nitrone, N-phenyl nitrone and their hydroxylamine tautomers (vinyl-hydroxylamine, N-methyl-vinyl-hydroxylamine and N-phenyl-vinyl-hydroxylamine) on the reconstructed C(100)-2 x 1 surface have been investigated using hybrid density functional theory (B3LYP), Moller-Plesset second-order perturbation (MP2) and multi-configuration complete-active-space self-consistent-field (CASSCF) methods. The calculations showed that all the nitrones can react with the surface "dimer" via facile 1.3-dipolar cycloaddition with small activation barriers (less than 12.0 kJ/mol at B3LYP/6-31g(d) level). The [2+2] cycloaddition of hydroxylamine tautomers on the C(100) surface follows a diradical mechanism. Hydroxylamine tautomers first form diradical intermediates with the reconstructed C(I 00)-2 x I surface by overcoming a large activation barrier of 50-60 kJ/mol (B3LYP), then generate [2+2] cycloaddition products via diradical transition states with negligible activation barriers. The surface reactions result in hydroxyl or amino-terminated diamond surfaces, which offers new opportunity for further modifications. (C) 2007 Elsevier B.V. All rights reserved.