摘要
Reduction of the {Co(NO)} 8 cobalt-nitrosyl N-confused porphyrin (NCP) [Co(CTPPMe)(NO)] (1) produced electron-rich {Co(NO)} 9 [Co(CTPPMe)(NO)][Co(Cp∗) 2 ] (2), which was necessary for NO-to-N 2 O conversion. Complex 2 was NO-reduction-silent in neat THF, but was partially activated to a hydrogen-bonded species 2....MeOH in THF/MeOH (1:1, v/v). This species coupling with 2 transformed NO into N 2 O, which was fragmented from an [N 2 O 2 ]-bridging intermediate. An intense IR peak at 1622cm -1 was ascribed to ν(NO) in an [N 2 O 2 ]-containing intermediate. Time-course ESI(-) mass spectra supported the presence of the dimeric [Co(NCP)] 2 (N 2 O 2 ) intermediate. Five complete NO-to-N 2 O conversion cycles were possible without significant decay in the amount of N 2 O produced. Alcohol can H....elp: Water, methanol, or ethanol triggered the formation of a [N 2 O 2 ]-bridged intermediate from a reduced cobalt-nitrosyl N-confused porphyrin to enable the conversion of NO into N 2 O (see scheme). Hydrogen-bonding interactions assisted N-N coupling and N-O bond cleavage in the intermediate to generate N 2 O.