Synthesis, characterization and electrocatalytic H2 production of diiron complexes containing SeNC donors

Publication date: 1 July 2018 Source:Journal of Organometallic Chemistry, Volume 866 Author(s): Jin-Ping Li, Yao-Cheng Shi The three-component reactions of ArNHC(=Se)OCH3, Et3N and Fe3(CO)12 afford the [Et3NH]+ salt of the (μ-ArN=COCH3)Fe2(CO)6(μ-Se-) cluster anion. The Se-centered cluster anion reacts with CH3I to give two pairs of isomers (μ-k2N,C-ArN=COR)Fe2(CO)6(μ-SeCH3) (1-e, 1-a, Ar = C6H5) and (μ-k2N,C-ArN=COR)Fe2(CO)6(μ-SeCH3) (2-e, 2-a, Ar = 4-ClC6H4). Furthermore, trapping the Se-centered cluster anion (μ-ArN=COR)Fe2(CO)6(μ-Se-) with PPh2Cl offers (μ-k2N,C-ArN=COR)Fe2(CO)6(μ-k2Se,P-SePPh2) (3, Ar = C6H5, 5, Ar = 4-ClC6H4, R = CH3; 4, Ar = C6H5, 6, Ar = 4-ClC6H4, R = CH2Ph). Reactions of 1 with monophosphine L lead to the corresponding substituted complexes (μ-k2N,C-PhN=COCH3)Fe2(CO)5(L)(μ-SeCH3) (7-e, 7-a, L = PPh3; 8-e, L = PPh2Py). All the new complexes have been completely characterized by elemental analyses, IR, 1H NMR, 13C NMR, and 31P NMR spectroscopy and structurally determined by X-ray crystallography. Electrochemical studies reveal that when using HOAc or TFA as a proton source, all of the complexes can catalyze H2 production.
Source: Journal of Organometallic Chemistry - Category: Chemistry Source Type: research