Rapid, Reversible, Solid鈥揋as and Solution-Phase Insertion of CO2 into In鈥揚 Bonds

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• 作者：Diane A. Dickie ; Madeline T. Barker ; Michael A. Land ; Kira E. Hughes ; Jason A. C. Clyburne ; Richard A. Kemp
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：December 7, 2015
• 年：2015
• 卷：54
• 期：23
• 页码：11121-11126
• 全文大小：352K
• ISSN：1520-510X

文摘

The P,P-chelated heteroleptic complex bis[bis(diisopropylphosphino)amido]indium chloride [(i-Pr₂P)₂N]₂InCl was prepared in high yield by treating InCl₃ with 2 equiv of (i-Pr₂P)₂NLi in Et₂O/tetrahydrofuran solution. Samples of [(i-Pr₂P)₂N]₂InCl in a pentane slurry, a CH₂Cl₂ solution, or in the solid state were exposed to CO₂, resulting in the insertion of CO₂ into two of the four M鈥揚 bonds to produce [O₂CP(i-Pr₂)NP(i-Pr₂)]₂InCl in each case. Compounds were characterized by multinuclear NMR and IR spectroscopy, as well as single-crystal X-ray diffraction. ReactIR solution studies show that the reaction is complete in less than 1 min at room temperature in solution and in less than 2 h in the solid鈥揼as reaction. The CO₂ complex is stable up to at least 60 掳C under vacuum, but the starting material is regenerated with concomitant loss of carbon dioxide upon heating above 75 掳C. The compound [(i-Pr₂P)₂N]₂InCl also reacts with CS₂ to give a complicated mixture of products, one of which was identified as the CS₂ cleavage product [S鈺怭(i-Pr₂)NP(i-Pr₂)]₂InCl]₂(渭-Cl)[渭-(i-Pr₂P)₂N)].