INVOLVEMENT OF IRON ALKYL COMPLEXES AND ALKYL RADICALS IN THE KHARASCH REACTIONS - PROBING THE CATALYSIS USING IRON PHOSPHINE COMPLEXES

被引：20

作者：

EVANS, DJ ^{[1
]}

HENDERSON, RA ^{[1
]}

HILLS, A ^{[1
]}

HUGHES, DL ^{[1
]}

OGLIEVE, KE ^{[1
]}

机构：

[1] UNIV SUSSEX,AFRC,INST PLANT SCI RES,NITROGEN FIXAT LAB,BRIGHTON BN1 9RH,E SUSSEX,ENGLAND

来源：

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1992年 / 07期

关键词：

D O I：

10.1039/dt9920001259

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The X-ray crystal structure of trans-[FeBr2(depe)2] (depe = Et2PCH2CH2PEt2) has been determined, and its catalysis of the reactions between MgBrEt and RBr (R = Et, Pr(n), Bu(n), PhCH2 or H2CCHCH2) to give alkanes and alkenes investigated. Detailed analysis of the products and the time courses of the reactions demonstrate that the hydrido-species trans-[FeH(Br)(depe)2]n+ (n = 0 or 1) are not intermediates in the reaction, but are products formed in the termination steps. It is shown that the catalysis can proceed by one of two pathways, depending on the alkyl halide. One pathway is proposed to involve the intermediacy of iron(I) species, and the other of iron(III) complexes. Both catalytic cycles contain the same fundamental reaction: the abstraction of a beta-hydrogen atom from a [FeEt(Br)(depe)2]n+ species by alkyl radicals to give the alkane and ethylene. The X-ray crystal structure of trans-[FeH(Br)(depe)2]BPh4 is reported.

引用

页码：1259 / 1265

页数：7

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