DEUTERIUM SUBSTITUTION OF THIOPHENES BY D2 - CATALYTIC ROLE OF A HYDROSULFIDO-BRIDGED MOLYBDENUM COMPLEX

被引：20

作者：

LOPEZ, L ^{[1
]}

GODZIELA, G ^{[1
]}

DUBOIS, MR ^{[1
]}

机构：

[1] UNIV COLORADO,DEPT CHEM & BIOCHEM,BOULDER,CO 80309

来源：

ORGANOMETALLICS | 1991年 / 10卷 / 08期

关键词：

D O I：

10.1021/om00054a029

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The cationic complex [(MeCpMo)2(S2CH2)(mu-S)(mu-SH)]SO3CF3 (1; Cp' = MeCp = C5H4CH3) catalyzed the deuterium substitution of thiophene, methylthiophenes, and benzothiophene in dichloromethane solution at D2 pressures of 3-4 atm and temperatures of 25-70-degrees-C. Substitution patterns were similar to those observed for deuteration reactions carried out over sulfided molybdenum surfaces. Possible roles for 1 in the homogeneous catalytic reaction have been investigated. Evidence has been observed for the activation of D2 by 1; when 1 was stirred under a mixture of H2/D2, HD was produced. However, no evidence for the interaction of 1 with thiophenes has been observed. A mechanism has been proposed for the thiophene deuteration, which involves the conversion of D2 to D+ by 1, followed by the electrophilic aromatic substitution of D+ on thiophenes. Substitution patterns and kinetic information are consistent with an acid-exchange pathway. Implications of this mechanism for the surface-catalyzed reactions are discussed.

引用

页码：2660 / 2664

页数：5

共 40 条

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