Bioinspired CNP Iron(II) Pincers Relevant to [Fe]-Hydrogenase (Hmd): Effect of Dicarbonyl versus Monocarbonyl Motifs in H Activation and Transfer Hydrogenation.

A set of bioinspired carbamoyl CNP pincer complexes are reported that are relevant to [Fe]-hydrogenase (Hmd). The species [(CNP)Fe(CO)I] [R = Ph, ; R = Pr, ] undergoes ligand deprotonation, resulting in the dearomatized complexes of formulas [(CNP)Fe(CO)] ( and ). The crystal structure and H{P} NMR spectroscopy of the iodide-bound dearomatized species [Na(18-crown-6)][(CNP)Fe(CO)I] () showed that the deprotonated moiety was the phosphoramine N(H) linkage.

Detection of CO in the Electrochemical Reduction of Carbon Dioxide in N,N-Dimethylformamide by Scanning Electrochemical Microscopy.

The electrocatalytic reduction of CO has been studied extensively and produces a number of products. The initial reaction in the CO reduction is often taken to be the 1e formation of the radical anion, CO. However, the electrochemical detection and characterization of CO is challenging because of the short lifetime of CO, which can dimerize and react with proton donors and even mild oxidants.