1,2 addition or cycloaddition of allenes by a dihafnium μ−Nitrido complex? A DFT study

Publication date: Available online 27 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Pengjie Li, Longfei Li, Xin Yue, Qianyue Wang, Min Pu, Zuoyin Yang, Ming LeiAbstractThe reaction mechanisms of the hydrogenation of [(η5-C5H2-1,2,4-Me3)2Hf]2(NCO) (μ2-N) (1) were studied using density functional theory (DFT) method. The calculated results indicate that the first step is the addition of H2 to the HfN double bond, the second step is the insertion of isocyanate into the bridging metal hydride. The metal centers with a low electronegativity benefits the hydrogenation of 1. Then the reaction mechanisms of allenes with 1 were also investigated. The calculated results imply that the allenes with larger hindrance tend to undergo 1,2 addition with 1, the allenes with smaller hindrance tend to undergo 2 + 2 cycloaddition with 1, which is in good agreement with experimental results.Graphical abstract

Source: Journal of Organometallic Chemistry - August 29, 2018 Category: Chemistry Source Type: research