RATE CONSTANTS AND ARRHENIUS PARAMETERS FOR THE REACTION OF ACYL RADICALS WITH BU(3)SNH AND (ME(3)SI)(3)SIH

被引：55

作者：

CHATGILIALOGLU, C

FERRERI, C

LUCARINI, M

PEDRIELLI, P

PEDULLI, GF

机构：

[1] UNIV NAPLES FEDERICO II,DIPARTIMENTO CHIM ORGAN & BIOL,I-80134 NAPLES,ITALY

[2] UNIV BOLOGNA,DIPARTIMENTO CHIM ORGAN A MANGINI,I-40127 BOLOGNA,ITALY

来源：

ORGANOMETALLICS | 1995年 / 14卷 / 06期

关键词：

D O I：

10.1021/om00006a013

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The kinetics of hydrogen abstraction from Bu(3)SnH and (Me(3)Si)(3)SiH by a variety of acyl radicals have been studied in nonpolar solvents over a range of temperatures by using competing decarbonylation reactions. The relative preexponential factors are essentially independent of the nature of the acyl radical and of the hydride; i.e. log(A(d)/A(MH)) congruent to 4.8. On the other hand, the relative activation energies, i.e. E(d) - E(MH), decrease by ca. 2 kcal mol(-1) on going from primary to secondary and also on going from secondary to tertiary substituents at the carbonyl moiety for a particular hydride. As one goes from Bu(3)SnH to (Me(3)Si)(3)SiH for a particular acyl radical, the E(d) - E(MH) also decreases by ca. 2 kcal mol(-1). Combining our relative kinetic data with the gas-phase Arrhenius parameters for the propanoyl radical decarbonylation allows for the evaluation of the absolute Arrhenius expressions for the reactions of acyl radicals with Bu(3)SnH and (Me(3)Si)(3)SiH and for the decarbonylation of secondary and tertiary acyl radicals. Rate constants at 80 degrees C for the reactions of (Me(3)Si)(3)Si-. and Bu3Sn(.) radicals with acyl derivatives have also been estimated.

引用

页码：2672 / 2676

页数：5

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