Coordination chemistry of high oxidation nitrogen containing amides and heterocycles

The catalytic reduction of nitrous oxide (N2O) to dinitrogen (N2) by nitrous oxide reductase (N2OR) is poorly understood. The N2O molecule is a poor ligand with relatively sparse coordination chemistry. We proposed the synthesis of probable nitrous oxide precursors which can be coordinated to transition metals prior to conversion to nitrous oxide. Nitramide, H2NNO2, 2-1, and the related nitrogen amide acids N-nitroamide 2-2, 2-3; N-nitrocarbamate 2-4, 2-5, N-nitrosocarbamate 2-6, 2-7; N-nitrosulfonamide 2-8 have been synthesized as possible nitrous oxide precursors for coordination studies with transition metals. The silver salts of the conjugate base of the nitrogen acids N-nitroamide 2-2Ag; N-nitrocarbamate 2-4Ag, 2-5Ag; N-nitrosocarbamate 2-6Ag; N-nitrosulfonamide 2-8Ag are synthesized from the reaction of the acids with Ag2CO3. Similarly the potassium salts of the nitrogen acids N-nitroamide 2-2K; N-nitrocarbamate 2-4K; N-nitrosocarbamate 2-6K; N-nitrosulfonamide 2-8K are synthesized from the reaction of the nitrogen acids with K2CO3 or CH3OK. To investigate the pi-acidity of the nitrogen acids, a series of Ir(I) complexes of the nitrogen acids, trans-Ir(η1-X)(CO)(PPh3)2, (X = nitrogen acid) N-nitroamide 3-3; N-nitrocarbamate 3-4, 3-5; N-nitrosocarbamate 3-6; N-nitrosulfonamide 3-7 are synthesized from the reaction of Vaska's complex, trans-Ir(Cl)(CO)(PPh3)2 (3-1) with the silver salts of the conjugate base of the nitrogen acids (N-nitroamide 2-2Ag; N-nitrocarbamate 2-4Ag, 2-5Ag; N-nitrosocarbamate 2-6Ag; N-nitrosulfonamide 2-8Ag). Comparative studies with the related amides, dinitramide and bistriflimide, have also been done.The oxidative addition of the nitrogen acids (N-nitroamide 2-2, 2-3; N-nitrocarbamate 2-4, 2-5) to trans-Ir(Cl)(N2)(PPh3)2 (3-2) afford the Ir(III) complexes of the nitrogen acids, Ir(η2-X)(H)(Cl)(PPh3)2, (X = nitrogen acid) N-nitroamide 3-11, 3-12; N-nitrocarbamate 3-13, 3-14. The 31P, 1H NMR and IR spectroscopic reaction monitoring profiles of the oxidative addition reactions give evidence of reaction intermediates that eventually convert to the final product. The reaction of 3-11 with CO and P(CH3)2Ph result in the formation of multiple isomers of the addition products and also phosphine substitution. Addition of methyl triflate to 3-11 in CH3CN is found to result in the substitution and loss of the nitrogen acid. The Re(I) complexes of the nitrogen acids , trans-Re(η2-X)(CO)2(PPh3)2, (X = nitrogen acid) N-nitroamide 4-8; N-nitrocarbamate 4-9; N-nitrosulfonamide 4-12 are synthesized from the reaction of trans-[Re(CH3CN)2(CO)2(PPh3)2](Y), (Y = ClO4: 4-3, BF4: 4-7) with the potassium salts of the conjugate base of the nitrogen acids 2-2K, 2-4K and 2-8K respectively. The reaction of 4-7 with N-nitrosocarbamate 2-6K at room temperature gives mostly the kinetic isomer trans-Re(η2-X)(CO)2(PPh3)2 (4-10). The same reaction at reflux conditions gives mostly a thermodynamic isomer Re(η2-X)(CO)2(PPh3)2 (4-11A). Complex 4-9 and 4-10 are found to crystallize in an unusual space group R-3 that gives a large unit cell with huge solvent channels between the Re complexes and CH2Cl2 solvate molecules. The Dimroth/amidine rearrangement of benzotriazoles has been shown to exist in solution for 5-1 by variable temperature 19F NMR. The reaction of 3-2 with the benzotriazoles 5-1 and 5-2 gives the new Ir(I) complex, trans-Ir(Cl)(η1-5-1)(PPh3)2 (5-7) and Ir(III) complex, trans-Ir(Cl)(η3-5-2)(PPh3)2 (5-8) respectively. Complex 5-7 undergoes addition and substitution reactions readily to give multiple isomers while 5-8 is inert towards nucleophiles.

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