Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N–C)(CO)3] complexes

Autor:	Jay Agarwal, Travis W. Shaw, Charles J. Stanton, George Majetich, Andrew Bruce Bocarsly, Jonathon E. Vandezande, Henry F. Schaefer
Rok vydání:	2015
Předmět:	Electrolysis Ligand Cyanide Electrochemistry Photochemistry Catalysis law.invention Inorganic Chemistry chemistry.chemical_compound Crystallography chemistry law Saturated calomel electrode Carbene
Zdroj:	Dalton Transactions. 44:2122-2131
ISSN:	1477-9234 1477-9226
Popis:	The synthesis, electrochemical activity, and relative photodecomposition rate is reported for four new Mn(i) N-heterocyclic carbene complexes: [MnX(N-ethyl-N'-2-pyridylimidazol-2-ylidine)(CO)3] (X = Br, NCS, CN) and [MnCN(N-ethyl-N'-2-pyridylbenzimidazol-2-ylidine)(CO)3]. All compounds display an electrocatalytic current enhancement under CO2 at the potential of the first reduction, which ranges from -1.53 V to -1.96 V versus the saturated calomel electrode. Catalytic CO production is observed for all species during four-hour preparative-scale electrolysis, but substantial H2 is detected in compounds where X is not Br. All species eventually decompose under both 350 nm and 420 nm light, but cyanide substituted complexes (X = CN) last significantly longer (up to 5×) under 420 nm light as a result of a blue-shifted MLCT band.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::b8d9625fcfe0018f6c29a19dddad937e https://doi.org/10.1039/c4dt03079f Zobrazit plný text záznamu