[Ir(COD)(diphos)Cl配合物活化sp^3 C-H键及其促进CO、CO2插入Ir-C键反应性能的研究

本文利用[Ir(COD)(μ-Cl)]2与双膦螯合配位体之间的反应合成了三个新的配合物[Ir(COD)(diphos)]Cl(diphos=dmpe、depe、dppe),用IR、NMR、电导和元素分析测定了结构.以CH3CN为反应底物分别考察了它们活化sp^3C-H键的能力及其反应规律.在此基础上进一步研究了使CO、CO2插入生成的Ir-CH2CN键的可能性.结果表明:在温和条件下进行这一插入反应是可能的,并用光谱方法证实有相应的含羰基、羧基的金属配合物的生成.

Activation of C-H bond and insertion reaction of CO,CO2 into Ir-C bond promoted by (Ir(COD) (diphos))Cl complexes

Three new organoiridium complexes, [Ir(COD)(diphos)]Cl (diphos = R2PCH2CH2PR2, R = Me, Et, Ph; COD = cyclooctadiene) are synthesized from [Ir(COD)(m-Cl)]2 and diphosphine in molar ratio 1:2, and characterized by means of IR, 1H NMR, elec. conductivity and elemental analyses. The reactions of these complexes with MeCN in the presence of CO or CO2 gave [(H)Ir(diphos)(CO)2(COCH2CN)]Cl or products containing Ir-OCOR groups suggest that these complexes are able to activate the C-H bonds of MeCN and promote the insertion reaction of CO, CO2 with the Ir-C bond.