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Selective Alkene Insertion into Inert Hydrogen–Metal Bonds Catalyzed by Mono(phosphorus ligand)palladium(0) Complexes
Organometallics ( IF 2.8 ) Pub Date : 2017-10-17 00:00:00 , DOI: 10.1021/acs.organomet.7b00593
Nobuyuki Komine 1 , Ryo Ito 1 , Hiromi Suda 1 , Masafumi Hirano 1 , Sanshiro Komiya 1
Affiliation  

Isolated mono(phosphorus ligand)palladium(0) complexes catalyzed alkene insertions into hydrogen–tungsten bonds. These insertions using WHCp(CO)3 with ethyl acrylate and dimethyl fumarate smoothly gave the corresponding alkyltungsten complexes. Kinetic studies involving the stoichiometric reactions and DFT calculations suggest the following steps: (i) formation of a mono(phosphorus ligand)mono(alkene)palladium(0) species, (ii) subsequent reaction of a metal hydride with the palladium(0), (iii) insertion of the coordinated alkene into the resulting palladium hydride, and (iv) reductive elimination between the alkyl and metal on the palladium center to release the alkylmetal species with regeneration of a palladium(0) by a reaction with alkene.

中文翻译:

单(磷配体)钯(0)​​配合物催化将烯烃选择性插入惰性氢金属键中

孤立的单(磷配体)钯(0)​​络合物催化烯烃插入氢-钨键中。使用WHCp(CO)3与丙烯酸乙酯和富马酸二甲酯进行的这些插入操作顺利生成了相应的烷基钨络合物。涉及化学计量反应和DFT计算的动力学研究建议采取以下步骤:(i)形成单(磷配体)单(烯烃)钯(0)​​物种,(ii)金属氢化物与钯(0)的后续反应;(iii)将配位烯烃插入所得的氢化钯中,以及(iv)通过钯与烯烃的反应再生钯(0),从而在钯中心上的烷基与金属之间进行还原性消除,从而释放出烷基金属。
更新日期:2017-10-17
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