Andrews Lester
Department of Chemistry, University of Virginia, P. O. Box 400319, Charlottesville, VA 22904-4319, USA.
Chem Soc Rev. 2004 Feb 20;33(2):123-32. doi: 10.1039/b210547k. Epub 2004 Jan 30.
Metal hydrides are of considerable importance in chemical synthesis as intermediates in catalytic hydrogenation reactions. Transition metal atoms react with dihydrogen to produce metal dihydrides or dihydrogen complexes and these may be trapped in solid matrix samples for infrared spectroscopic study. The MH(2) or M(H(2)) molecules so formed react further to form higher MH(4), (H(2))MH(2), or M(H(2))(2), and MH(6), (H(2))(2)MH(2), or M(H(2))(3) hydrides or complexes depending on the metal. In this critical review these transition metal and dihydrogen reaction products are surveyed for Groups 3 though 12 and the contrasting behaviour in Groups 6 and 10 is discussed. Minimum energy structures and vibrational frequencies predicted by Density Functional Theory agree with the experimental results, strongly supporting the identification of novel binary transition metal hydride species, which the matrix-isolation method is well-suited to investigate. 104 references are cited.
金属氢化物在化学合成中作为催化氢化反应的中间体具有相当重要的意义。过渡金属原子与氢气反应生成金属二氢化物或二氢配合物，这些产物可被捕获在固体基质样品中用于红外光谱研究。如此形成的MH₂或M(H₂)分子会进一步反应，根据金属的不同形成更高阶的MH₄、(H₂)MH₂或M(H₂)₂，以及MH₆、(H₂)₂MH₂或M(H₂)₃氢化物或配合物。在这篇综述中，对第3族至第12族的这些过渡金属与氢气的反应产物进行了综述，并讨论了第6族和第10族中截然不同的行为。密度泛函理论预测的最低能量结构和振动频率与实验结果相符，有力地支持了新型二元过渡金属氢化物物种的鉴定，而基质隔离法非常适合研究这些物种。引用参考文献104篇。
