Metal or Nonmetal Cooperation with a Phenyl Group: Route to Catalysis? A Computational Investigation

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• 作者：Kamalika Ghatak ; Manoj Mane ; Kumar Vanka
• 刊名：ACS Catalysis
• 出版年：2013
• 出版时间：May 3, 2013
• 年：2013
• 卷：3
• 期：5
• 页码：920-927
• 全文大小：452K
• 年卷期：v.3,no.5(May 3, 2013)
• ISSN：2155-5435

文摘

Full quantum mechanical calculations demonstrate that cooperativity in the form of the activation of the M鈥揅 bond (M: transition metal or boron, C: the ipso carbon of the coordinated phenyl group) can lead to effective catalysis pathways. Calculations show that the presence of an aromatic bidentate ligand attached to a transition metal, or even a main group element, such as boron, can lead to effective catalysts for a range of important reactions, such as the dehydrogenation of ammonia borane and formic acid and the activation of the N鈥揌 bond in aromatic amines. Moreover, it is shown that the design of tridentate pincer complexes with the aromatic group at a terminal end can lead to effective M鈥揅 cooperativity. As such, the current work introduces a new concept in cooperativity and bond activation chemistry.

Keywords:

metal鈭抣igand cooperativity; catalysis; density functional theory; small molecule activation