STABLE HOMOLEPTIC METAL ALKYLS
STABLE HOMOLEPTIC METAL ALKYLS
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稳定的均配金属烷基
DOI：
10.1021/ar50079a001
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发表时间：
1974
影响因子：
18.3
通讯作者：
R. Pearce
中科院分区：
文献类型：
--
作者：
P. Davidson;M. Lappert;R. Pearce
自从Frankland于1849年发现了自燃的ZnEt2以来，金属烷基化合物就引起了人们的极大兴趣。相关问题的范围是巨大的，从理论或结构研究到有机化学或生物化学。一些化合物，特别是缺电子的烷基化合物，如(LiM)4，(BeMe2U，和(AlMe3)2)，已经提供了共价分子的重要例子(与B2H6一起)，其中简单的两电子双中心成键模型显然是不合适的。许多衍生物在合成试剂中起着关键作用，特别是锂、锌、汞、铝、锡和铜的格氏和烷基。过渡金属烷基是金属催化的烯烃或乙炔反应的重要中间体，其中一些在石油化工、聚合物或重有机化工中是重要的，如Ziegler-Natta聚合中的钛的烷基和CO(CO)3氢甲酰化反应中的钴的烷基。几种主要的金属烷基在工业上有很大的用途：PbEt4作为抗爆汽油添加剂；SNIV化合物作为聚氯乙烯的稳定剂和杀菌剂；有机硅作为橡胶、树脂或纸张和纺织品整理剂；以及A1衍生物在异戊二烯或长链醇的制造中的应用。维生素B12辅酶提供了一个天然存在的金属烷基的独特例子，它的Com-C键的分裂涉及到它所控制的具有生物学意义的酶异构化反应。
Since Frankland’s discovery in 1849 of the spontaneously inflammable ZnEt2, metal alkyls have been of considerable interest. The scope of relevant problems is immense, ranging fromtheoretical or struc-tural studies to organic or biological chemistry. Sev-eral compounds, especially the electron-deficient al-kyls such as (LiMe) 4,(BeMe2U, and (AlMe3) 2, have provided significant examples (along with B2H6) of covalent molecules in which a simple two-electron two-center bonding model is demonstrably inadequate. Many derivatives have a key role as synthetic reagents, notably the Grignards and alkyls of Li, Zn, Hg, Al, Sn, and Cu. Transition metal alkyls are vital intermediates in metal-catalyzed reactions of olefins or acetylenes, some of which are important inpetro-chemical, polymer, or heavy organic chemical indus-try, eg, alkyls of Ti in Ziegler-Natta polymerizations and of Co in hydroformylation usingCo2 (CO) 3. Several main group metal alkyls have large tonnage industrial use: PbEt4 as an antiknock gasoline additive; SnIV compounds as stabilizers for poly (vinyl chloride) and as fungicides or germicides; silicones as rubbers, resins, or paper and textile finishes; and A1 derivatives in the manufacture of isoprene or longchain alcohols. Vitamin B12 coenzyme provides a unique example of a naturally occurring metal alkyl, and fission ofits Com-C bond is implicated in the biologically important enzymatic isomerization reac-tions which it controls.