Activation of Nitrogen Br酶nsted Acids: Synthesis and Reactivity of a New Class of Nitrogen Acid Complexes

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• 作者：D. Scott Bohle ; Zhijie Chua
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：October 20, 2014
• 年：2014
• 卷：53
• 期：20
• 页码：11160-11172
• 全文大小：697K
• ISSN：1520-510X

文摘

The nitrogen acids RC(O)NHNO₂, N-nitroamide, R = CH₃ (1), C₂H₅ (2) and N-nitrocarbamate, R鈥睴C(O)NHNO₂, R鈥?= CH₃ (3), C₂H₅ (4) are a class of primary N-nitrocarboxamide compounds that oxidatively add to trans-Ir^(I)(Cl)(N₂)(PPh₃)₂ to give six-coordinate Ir^(III)(畏²-(NO₂)-nitrogen acid)(H)(Cl)(PPh₃)₂ complexes 5鈥?b>8. Unexpected fluxional behavior of the complexes in solution is observed by ¹H NMR spectroscopy. Reaction intermediates of the oxidative addition reactions were also observed and monitored using ³¹P and ¹H NMR and solution IR spectroscopies. Complex 5 reacts with methyl triflate in CH₃CN to generate bis(acetonitrile) complex (9) from a net loss of the nitrogen acid anion. P(CH₃)₂Ph reacts with 5 to give phosphine-substituted and P(CH₃)₂Ph addition isomers (10). Reactivity studies of 5 with CO gave metastable CO adduct isomer 11, which loses CO on prolonged standing in solution.