Activation of Nitrogen Brønsted Acids: Synthesis and Reactivity of a New Class of Nitrogen Acid Complexes
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posted on 2014-10-20, 00:00 authored by D. Scott Bohle, Zhijie ChuaThe nitrogen acids RC(O)NHNO2, N-nitroamide, R = CH3 (1), C2H5 (2) and N-nitrocarbamate, R′OC(O)NHNO2, R′ = 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)(η2-(NO2)-nitrogen acid)(H)(Cl)(PPh3)2 complexes 5–8. 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.
