Gas phase basicity of silanaldehydes and silanones

被引：3

作者：

Audier, HE ^{[1
]}

Fossey, J ^{[1
]}

Denhez, JP ^{[1
]}

Jacquet, JP ^{[1
]}

Mourgues, P ^{[1
]}

机构：

[1] Ecole Polytech, Lab Mechanismes Reactionnels, UMR 7651, CNRS, F-91128 Palaiseau, France

来源：

INTERNATIONAL JOURNAL OF MASS SPECTROMETRY | 2003年 / 227卷 / 03期

关键词：

gas basicity; proton affinity; silanones; silanaldehydes; kinetic method; proton-bound dimer; calculation;

D O I：

10.1016/S1387-3806(03)00089-7

中图分类号：

O64 [物理化学（理论化学）、化学物理学]; O56 [分子物理学、原子物理学];

学科分类号：

070203 ; 070304 ; 081704 ; 1406 ;

摘要：

Gas basicities (GBs) and proton affinities (PAs) of CH3SiH=O, CH3CH2SiH=O, (CH3)(2)Si=O (CH3CH2)(2)Si=O, were determined by using the kinetic method as well as calculations. From experiment, GB of these molecules were respectively measured to be 203.3, 206.3, 213.4 and 218.0 kcal mol(-1). The precision is estimated to be 0.5 kcal mol(-1). Calculations are in excellent agreement with experiment. GB and PA of the R1R2Si=O compounds are far above those of their counterparts R1R2C=O, containing exclusively carbon. The difference lies between 25 and 30 kcal mol(-1) and slightly decreases as the substitution degree of silicon increases. This behavior strongly contrasts with that of silanols or silanamines whose GB and PA are close to those of the corresponding alcohols or amines. This can be explained by the high DeltaH(f) of neutral low coordinate molecules containing silicon. (C) 2003 Elsevier Science B.V All rights reserved.

引用

页码：381 / 389

页数：9

共 34 条

[1]

ADAMS NG, 1988, TECHNIQUES STUDY ION, P165

[2]

AUDIER HE, IN PRESS

[3]

AUIER HE, 1998, P 49 ASMS C MASS SPE

[4] A relationship between the kinetics and thermochemistry of proton transfer reactions in the gas phase [J].

Bouchoux, G ;

Salpin, JY ;

Leblanc, D .

INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES, 1996, 153 (01) :37-48

[5] A FOURIER TRANSFORM-ION CYCLOTRON-RESONANCE STUDY OF STERIC EFFECTS ON PROTON-TRANSFER REACTIONS OF POLYALKYL BENZENES [J].

BUKER, HH ;

GRUTZMACHER, HF .

INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES, 1991, 109 :95-104

[6] THE INFINITY CELL - A NEW TRAPPED-ION CELL WITH RADIOFREQUENCY COVERED TRAPPING ELECTRODES FOR FOURIER-TRANSFORM ION-CYCLOTRON RESONANCE MASS-SPECTROMETRY [J].

CARAVATTI, P ;

ALLEMANN, M .

ORGANIC MASS SPECTROMETRY, 1991, 26 (05) :514-518

[7]

COOKS RG, 1994, MASS SPECTROM REV, V13, P287

[8] GAUSSIAN-2 THEORY USING REDUCED MOLLER-PLESSET ORDERS [J].

CURTISS, LA ;

RAGHAVACHARI, K ;

POPLE, JA .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (02) :1293-1298

[9]

Frisch M.J., 1998, GAUSSIAN 98

[10] KINETIC AND THERMODYNAMIC CONSIDERATIONS OF THE BRACKETING METHOD - ENTROPY-DRIVEN PROTON-TRANSFER REACTIONS IN A FOURIER-TRANSFORM MASS-SPECTROMETER [J].

GORMAN, GS ;

AMSTER, IJ .

ORGANIC MASS SPECTROMETRY, 1993, 28 (12) :1602-1607

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