Gas-phase reactivity of organosilane radical cations. An FT-ICR study

被引：10

作者：

Chiavarino, B ^{[1
]}

Crestoni, ME ^{[1
]}

Fornarini, S ^{[1
]}

机构：

[1] Univ Roma La Sapienza, Dipartimento Studi Chim & Tecnol Sostanze Biologi, I-00185 Rome, Italy

来源：

ORGANOMETALLICS | 2000年 / 19卷 / 05期

关键词：

D O I：

10.1021/om990428a

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The bimolecular reactivity of organosilane radical cations (RSiMe3.+) toward selected based nucleophiles (N) has been studied in the gas phase by the FT-ICR technique. The two major reaction pathways are H+ and Me3Si+ transfer, whose branching ratio depends on the features of R and N. The onset for Me3Si+ transfer is close to its thermochemical threshold. Deprotonation of ionized benzyltrimethylsilane is unprecedented in solution but is highly efficient in the gas phase when a strong nitrogen base is used, suggesting a potentially useful route to obtain silylated radicals. The kinetic study of a model degenerate reaction suggests that the activation barrier for Me3Si+ transfer between oxygen centers is negligible, as observed for the corresponding proton-transfer process.

引用

页码：844 / 848

页数：5

共 44 条

[1] SIDE-CHAIN REACTIVITY OF AROMATIC RADICAL CATIONS [J].

BACIOCCHI, E .

ACTA CHEMICA SCANDINAVICA, 1990, 44 (07) :645-652

[2] A KINETIC-STUDY OF THE ELECTRON-TRANSFER-INITIATED CARBON SILICON BOND-CLEAVAGE REACTIONS OF BENZYLTRIALKYLSILANES PROMOTED BY 12-TUNGSTOCOBALT(III)ATE ION [J].

BACIOCCHI, E ;

CRESCENZI, M ;

FASELLA, E ;

MATTIOLI, M .

JOURNAL OF ORGANIC CHEMISTRY, 1992, 57 (17) :4684-4689

[3] CHLORANIL-SENSITIZED PHOTOLYSIS OF BENZYLTRIMETHYLSILANES - SOLVENT EFFECT ON THE COMPETITION BETWEEN CARBON-HYDROGEN AND CARBON-SILICON BOND-CLEAVAGE [J].

BACIOCCHI, E ;

DEL GIACCO, T ;

ELISEI, F ;

IOELE, M .

JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (24) :7974-7983

[4] ONE-ELECTRON OXIDATION OF 2,2-DIMETHYL-2-SILAINDANE BY POTASSIUM 12-TUNGSTOCOBALTATE(III) - LACK OF EVIDENCE FOR STEREOELECTRONIC EFFECTS ON THE CLEAVAGE OF A BETA-CARBON SILICON BOND IN AN AROMATIC CATION-RADICAL [J].

BACIOCCHI, E ;

BERNINI, R ;

LANZALUNGA, O .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1993, (22) :1691-1692

[5] Homolytic vs heterolytic C-H bond cleavage in alkylaromatic radical cations. Formation of diarylmethyl cation in the photoinduced electron transfer reaction of bis(4-methoxyphenyl)methane sensitized by chloranil [J].

Baciocchi, E ;

Del Giacco, T ;

Elisei, F ;

Lanzalunga, O .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (45) :11800-11801

[6] EMPIRICAL-METHODS FOR DETERMINATION OF IONIZATION GAUGE RELATIVE SENSITIVITIES FOR DIFFERENT GASES [J].

BARTMESS, JE ;

GEORGIADIS, RM .

VACUUM, 1983, 33 (03) :149-153

[7] EFFECTS OF ALPHA-SILICON AND BETA-SILICON ATOMS ON THE FREE-ENERGIES OF C-H HOMOLYSIS AND HETEROLYSIS [J].

BAUSCH, MJ ;

GONG, Y .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (13) :5963-5964

[8]

BECERRA R, 1998, CHEM ORGANIC SILICON, V2

[9] AN RADICAL IONS .50. ORGANO-SILICON RADICAL CATIONS [J].

BOCK, H ;

KAIM, W .

ACCOUNTS OF CHEMICAL RESEARCH, 1982, 15 (01) :9-17

[10] ORGANOSILICON RADICAL CATIONS [J].

BOCK, H ;

SOLOUKI, B .

CHEMICAL REVIEWS, 1995, 95 (05) :1161-1190

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