Iridium(I) Complexes of π‑Acidic Carboxamides
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The silver salts of the conjugate bases of the nitrogen acids N-nitroacetamide (Ag[CH3C(O)NNO2] (1)), N-nitrocarbamate (Ag[R′OC(O)NNO2], R′ = CH3 (2), C2H5 (3)), N-nitrosomethylcarbamate (Ag[CH3OC(O)NNO] (4)), and N-nitro-p-tolylsulfonamide, (Ag[p-tolylSO2NNO2] (5)) react with trans-Ir(Cl)(CO)(PPh3)2 (Vaska’s complex) to give trans-Ir(η1-nitrogen acid)(CO)(PPh3)2 complexes (6–10). The related silver amides dinitramide and bistriflimide also react with trans-Ir(Cl)(CO)(PPh3)2, to give trans-Ir[η1-N(NO2)2](CO)(PPh3)2 (11) and the unusual silver adduct [trans-Ir(Cl)(CO)(PPh3)2][Ag[N(SO2CF3)2]] (12), respectively. The reaction of trimethylsilyl bistriflimide, prepared in situ from trimethylsilyl bromide and Ag[N(SO2CF3)2] in acetonitrile, and Ir(F)(CO)(PPh3)2 gives [trans-Ir(CH3CN)(CO)-(PPh3)2][N(SO2CF3)3] (13). The molecular structures of these complexes are all square planar, with the exception of 12, which is square pyramidal with the AgX ligand in the apical position. Complexes 6–9, 12, and 13 are stable to air in solution, while 10 and 11 are reactive toward oxygen.
