铱(Ⅲ)卟啉β-羟乙与基醛的碳氢键活化(英文)

Aldehydic Carbon-Hydrogen Bond Activation with Iridium(Ⅲ) Porphyrin β-Hydroxyethyl

铱(Ⅲ)卟啉β-羟乙基,IrⅢ(ttp)CH2CH2OH(ttp=5,10,15,20-二价阴离子tetratolylporphyrinato),发现选择性裂解芳醛的醛的碳-氢键和给铱酰基配合物。酰基铱配合物对羰基化和脱羰反应以及潜在的功能化研究的很好的候选材料。这碳-氢键的建议活化机理:通过初始的β-羟基消除IrⅢ(ttp)CH2CH2OH生成IrⅢ(ttp)OH,然后进行与醛的CH键的σ-键复分解发生。

Iridium（Ⅲ） porphyrin β-hydroxyethyl, IrⅢ（ttp）CH2CH2OH （ttp=5,10,15,20- tetratolylporphyrinato dianion）, was found to selectively cleave the aldehydic carbon-hydrogen bonds of aryl aldehydes giving iridium acyl complexes. Iridium acyl complexes are good candidates for the studies on carbonylation and decarbonylation reactions as well as potential functionalization. The carbon-hydrogen bond activation （CHA） is proposed to occur through the initial β-hydroxyl elimination of IrⅢ （ttp）CH2CH2OH to give IrⅢ（ttp）OH, which then undergoes σ-bond metathesis with the aldehydic C-H bond.