Institut für Anorganische Chemie, RWTH Aachen, Landoltweg 1, 52056 Aachen, Germany.
Angew Chem Int Ed Engl. 2013 May 10;52(20):5228-46. doi: 10.1002/anie.201208942. Epub 2013 Apr 5.
Organometallic allyl compounds are important as allylation reagents in organic synthesis, as polymerization catalysts, and as volatile metal precursors in material science. Whereas the allyl chemistry of synthetically relevant transition metals such as palladium and of the lanthanoids is well-established, that of main group metals has been lagging behind. Recent progress on allyl complexes of Groups 1, 2, and 12-16 now provides a more complete picture. This is based on a fundamental understanding of metal-allyl bonding interactions in solution and in the solid state. Furthermore, reactivity trends have been rationalized and new types of allyl-specific reactivity patterns have been uncovered. Key features include 1) the exploitation of the different types of metal-allyl bonding (highly ionic to predominantly covalent), 2) the use of synergistic effects in heterobimetallic compounds, and 3) the adjustment of Lewis acidity by variation of the charge of allyl compounds.
有机金属烯丙基化合物作为有机合成中的烯丙基化试剂、聚合催化剂以及材料科学中的挥发性金属前体，具有重要意义。虽然合成相关过渡金属（如钯）和镧系元素的烯丙基化学已经得到很好的确立，但主族金属的烯丙基化学却落后了。现在，第 1、2 和 12-16 族的烯丙基配合物的最新进展提供了更完整的图景。这是基于对金属-烯丙基键合相互作用在溶液和固态中的基本理解。此外，还对反应性趋势进行了合理化，并发现了新类型的烯丙基特异性反应模式。关键特征包括 1）利用不同类型的金属-烯丙基键合（高离子到主要共价键），2）在杂双金属化合物中利用协同效应，以及 3）通过改变烯丙基化合物的电荷来调节路易斯酸度。
