The addition of alkynes to a tetrasilyidisilene - Evidence for a biradical intermediate

被引：15

作者：

Gottschling, SE ^{[1
]}

Jennings, MC ^{[1
]}

Baines, KM ^{[1
]}

机构：

[1] Univ Western Ontario, Dept Chem, London, ON N6A 5B7, Canada

来源：

CANADIAN JOURNAL OF CHEMISTRY | 2005年 / 83卷 / 09期

关键词：

disilene; alkyne; cycloaddition; reaction mechanism; mechanistic probe;

D O I：

10.1139/v05-169

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The addition of two newly developed mechanistic probes, (trans,trans-2-methoxy-3-phenylcyclopropyl)ethyne (1) and (trans,trans-2-methoxy-1-methyl-3-phenylcyclopropyl)ethyne (2), to tetrakis(tert-butyldimethylsilyl)disilene (3) has been investigated. The addition of 1 to 3 gave [-[2-(cis-2-methoxy-3-phenylcyclopropylidene)vinyl]-1,1,2,2-tetrakis(tert-butyldimethylsilyl)disilane (5) as the major product; whereas addition of alkyne 2 to the disilene gave three stereoisomers of 1,1,2,2-tetrakis(tert-butyldimethylsilyl)-6-methoxy-5-methyl-7-phenyl-1,2-disilacyclohepta-3,4-diene (7-9) and 1, 1.2,2-tetrakis(tert-butyldimethylsilyl)-3-(trans,trans-2-methoxy-1-methyl-3-phenylcyclopropyl)- 1,2-disilacyclobut-3-ene (10) as the major products. The formation of cycloheptaallenes 7-9 provides convincing evidence that the addition of alkynes to tetrasilyldisilenes involves the formation of a biradical intermediate.

引用

页码：1568 / 1576

页数：9

共 59 条

[1] Addition of phenylacetylene to germasilenes [J].

Baines, KM ;

Dixon, CE ;

Langridge, JM ;

Liu, HW ;

Zhang, F .

ORGANOMETALLICS, 1999, 18 (11) :2206-2209

[2] REACTIONS OF A CYCLOTRISILANE WITH ALKYNES - SYNTHESIS AND FIRST CRYSTAL-STRUCTURE OF 1,2-DISILACYCLOBUT-3-ENES [J].

BELZNER, J ;

IHMELS, H ;

KNEISEL, BO ;

HERBSTIRMER, R .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1994, (17) :1989-1990

[3] Organometallic chemistry on silicon and germanium surfaces [J].

Buriak, JM .

CHEMICAL REVIEWS, 2002, 102 (05) :1271-1308

[4] MOLECULAR-DYNAMICS WITH COMBINED QUANTUM AND EMPIRICAL POTENTIALS - C2H2 ADSORPTION ON SI(100) [J].

CARMER, CS ;

WEINER, B ;

FRENKLACH, M .

JOURNAL OF CHEMICAL PHYSICS, 1993, 99 (02) :1356-1372

[5]

Chaubon MA, 1996, MAIN GROUP MET CHEM, V19, P145

[6] THE SYNTHESIS, PROPERTIES, AND REACTIVITIES OF STABLE COMPOUNDS FEATURING DOUBLE BONDING BETWEEN HEAVIER GROUP-14 AND GROUP-15 ELEMENTS [J].

COWLEY, AH ;

NORMAN, NC .

PROGRESS IN INORGANIC CHEMISTRY, 1986, 34 :1-63

[7]

DEYOUNG DJ, 1986, CHEM LETT, P883

[8] Cycloaddition reactions of aldehydes to tetramesityldisilene and tetramesitylgermasilene: Evidence for a biradical intermediate [J].

Dixon, CE ;

Hughes, DW ;

Baines, KM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (43) :11049-11053

[9] Reaction of group 14 dimetallenes with alkenes: Electron-rich alkenes [J].

Dixon, CE ;

Liu, HW ;

VanderKant, CM ;

Baines, KM .

ORGANOMETALLICS, 1996, 15 (26) :5701-5705

[10] The reaction of group 14 dimetallenes with alkenes: Electron-poor alkenes [J].

Dixon, CE ;

Cooke, JA ;

Baines, KM .

ORGANOMETALLICS, 1997, 16 (25) :5437-5440

← 1 2 3 4 5 6 →