二氢对(η6-芳烃)Mo(PMe3)3配合物的氧化加成：萘和蒽效应的起源

Oxidative addition of dihydrogen to (eta6-arene)Mo(PMe3)3 complexes: origin of the naphthalene and anthracene effects.

作者信息

Zhu Guang, Janak Kevin E, Figueroa Joshua S, Parkin Gerard

机构信息

Department of Chemistry, Columbia University, New York, New York 10027, USA.

出版信息

J Am Chem Soc. 2006 Apr 26;128(16):5452-61. doi: 10.1021/ja058107f.

DOI:10.1021/ja058107f

PMID:16620117

Abstract

In contrast to the benzene and naphthalene compounds (eta(6)-PhH)Mo(PMe(3))(3) and (eta(6)-NpH)Mo(PMe(3))(3), the anthracene complex (eta(6)-AnH)Mo(PMe(3))(3) reacts with H(2) to undergo a haptotropic shift and give the eta(4)-anthracene compound (eta(4)-AnH)Mo(PMe(3))(3)H(2). Density functional theory calculations indicate that the increased facility of naphthalene and anthracene to adopt eta(4)-coordination modes compared to that of benzene is a consequence of the fact that the Mo-(eta(4)-ArH) bonding interaction increases in the sequence benzene < naphthalene < anthracene, while the Mo-(eta(6)-ArH) bonding interaction follows the sequence benzene > naphthalene approximately anthracene.

摘要

与苯和萘化合物（η(6)-PhH）Mo(PMe(3))(3) 及（η(6)-NpH）Mo(PMe(3))(3) 不同，蒽配合物（η(6)-AnH）Mo(PMe(3))(3) 与 H(2) 反应会发生亲核转移，生成 η(4)-蒽化合物（η(4)-AnH）Mo(PMe(3))(3)H(2)。密度泛函理论计算表明，与苯相比，萘和蒽更易采用 η(4)-配位模式，这是因为 Mo-(η(4)-ArH) 键相互作用按苯 < 萘 < 蒽的顺序增强，而 Mo-(η(6)-ArH) 键相互作用则按苯 > 萘≈蒽的顺序变化。