ELECTRON-TRANSFER MECHANISMS FOR ORGANOMETALLIC INTERMEDIATES IN CATALYTIC REACTIONS
ELECTRON-TRANSFER MECHANISMS FOR ORGANOMETALLIC INTERMEDIATES IN CATALYTIC REACTIONS
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DOI：
10.1021/ar50082a006
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发表时间：
1974-01-01
影响因子：
18.3
通讯作者：
KOCHI, JK
中科院分区：
文献类型：
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作者：
KOCHI, JK
有机化合物中间体在许多有机和生物化学反应中起着重要的作用，特别是过渡金属配合物催化的反应。[1]虽然已经提出了一些定性的机制，但几乎没有关于碳和金属之间的键是如何在有机金属物种中形成和断裂的基本见解。有机反应机制通常以双电子变化（即电子对过程）为特征，无论它们是通过离子途径还是自由基途径进行。另一方面，在无机化学中，单电子变化（即电子转移过程）在各种氧化还原反应中得到了很好的建立。为了弥合这一二分法，我们认为电子转移的概念在有机金属中间体反应中应起比迄今所设想的更广泛的作用。2通过考察有机金属模型化合物的反应，强调了单电子过程在催化反应中的重要性。在这篇文章中，我们希望主要描述我们的研究，旨在探讨在有机金属中间体中烷基转移研究中出现的一些问题。
Organometallic intermediates play a crucial role in a variety of organic and biochemical reactions, par-ticularly those catalyzed by transition-metal com-plexes. 1 Although a number of qualitative mechanisms have been proposed, there is almost no fundamental insight into how bonds between carbon and metals are made and broken inorganometallic species. Organic reaction mechanisms are generally characterized by two-electron changes (ie, electron-pair processes), whether they proceed by ionic or free-radical pathways. In inorganic chemistry, on the other hand, one-electron changes (ie, electron-transfer processes) are well established in a variety of oxidation-reduction reactions. To bridge this dichot-omy, we have felt that the concept of electron transfer should play an even wider role in the reactions of organometallic intermediates than heretofore sus-pected. 2We have emphasized the importance of one-elec-tron processes in catalytic reactions by examining the reactions of organometallic model compounds. In this Account we wish to describe mainly our studies aimed at probing some of the problems presented in the study of alkyl transfers in organometallic inter-mediates.