Abstract
The intermolecular N-N coupling of NO in a dinitrosyl iron complex (DNIC) induced by hydrogen bond donors in the secondary coordination sphere to form N(2)O is reported. A family of complexes containing pendant anilines in the secondary coordination sphere were synthesized and characterized. Reduction of the {Fe(NO)(2)}(9) complex [Fe((PhNH)PDI)(NO)(2)][BPh(4)] (3) to the {Fe(NO)(2)}(10) Fe((PhNH)PDI)(NO)(2) (4) results in intermolecular N-N coupling to form N(2)O. Similar reactions of the control {Fe(NO)(2)}(9) complex [Fe((PhNMe)PDI)(NO)(2)][BPh(4)] (7), which does not have H-bonding groups in the secondary coordination sphere, do not result in N(2)O formation. The hydrogen bonding capabilities of the complexes were explored spectroscopically and computationally.