Ab Initio and DFT Studies of the Thermal Rearrangement of Trimethylsilyl(methyl)silylene: Remarkable Rearrangements of Silicon Intermediates

被引：4

作者：

Boo, Bong Hyun ^{[1
]}

Im, Suk ^{[2
]}

Lee, Sungyul ^{[2
]}

机构：

[1] Chungnam Natl Univ, Dept Chem, Taejon 305764, South Korea

[2] Kyung Hee Univ, Dept Appl Chem, Kyonggi Do 446701, South Korea

来源：

JOURNAL OF COMPUTATIONAL CHEMISTRY | 2010年 / 31卷 / 01期

关键词：

silylsilylene rearrangement; trimethylsilyl(methyl)silylene; product ratio; MP2; DFT; IRC; CORRELATED MOLECULAR CALCULATIONS; GAUSSIAN-BASIS SETS; CONSISTENT BASIS-SETS; WAVE-FUNCTIONS; DENSITY; PATH; SILYLENES; EXCHANGE; DISILENE; BORON;

D O I：

10.1002/jcc.21254

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A reaction scheme for the rearrangement of trimethylsilyl(methyl)silylene (Me3Si-Si-Me) discovered in a pioneering work of organosilicon chemistry (Wulff et al., J Am Chem Soc 1978, 100, 6236) was studied by the MP2 and DFT methods. We report a thermal reaction scheme for the rearrangement of Me3Si-Si-Me with the structures and energies of various Silicon species along the isomerization paths, that can account for the experimentally found product ratio. The experimental product ratio is in good agreement with the theoretical one derived from the Gibbs free energy changes calculated in the present study. (c) 2009 Wiley Periodicals, Inc. J Comput Chem 31: 154-163, 2010

引用

页码：154 / 163

页数：10

共 24 条

[1]

[Anonymous], REACTIVE INTERMEDIAT

[2] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[3] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[4] TRANSPOSITION - A NEW REARRANGEMENT OF ALPHA-SILYLSILYLENES INVOLVING DISILENE INTERMEDIATES [J].

BOO, BH ;

GASPAR, PP .

ORGANOMETALLICS, 1986, 5 (04) :698-707

[5] Ab initio and DFT studies of the thermal rearrangement of trimethylsilylsilylene [J].

Boo, Bong Hyun ;

Im, Suk ;

Park, Sungwoo ;

Lee, Sungyul .

ORGANOMETALLICS, 2008, 27 (09) :2123-2127

[6] Comment on Dunning's correlation-consistent basis sets - Comment [J].

Davidson, ER .

CHEMICAL PHYSICS LETTERS, 1996, 260 (3-4) :514-518

[7] GAUSSIAN-BASIS SETS FOR USE IN CORRELATED MOLECULAR CALCULATIONS .1. THE ATOMS BORON THROUGH NEON AND HYDROGEN [J].

DUNNING, TH .

JOURNAL OF CHEMICAL PHYSICS, 1989, 90 (02) :1007-1023

[8]

Frisch M. J., 2004, GAUSSIAN 03 REVISION

[9] THE PATH OF CHEMICAL-REACTIONS - THE IRC APPROACH [J].

FUKUI, K .

ACCOUNTS OF CHEMICAL RESEARCH, 1981, 14 (12) :363-368

[10]

Gaspar P.P., 1978, Reactive Intermediates, V1, P229

← 1 2 3 →