Premium
Effect of “X” Ligands on the Photocatalytic Reduction of CO 2 to CO with Re(pyridylNHC‐CF 3 )(CO) 3 X Complexes
Author(s) -
Shirley Hunter,
Sexton Thomas More,
Liyanage Nalaka P.,
Palmer C. Zachary,
McNamara Louis E.,
Hammer Nathan I.,
Tschumper Gregory S.,
Delcamp Jared H.
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000283
Subject(s) - chemistry , ligand (biochemistry) , reactivity (psychology) , cyclic voltammetry , dissociation (chemistry) , photocatalysis , carbene , photochemistry , aryl , absorption spectroscopy , excited state , catalysis , crystallography , medicinal chemistry , electrochemistry , organic chemistry , medicine , biochemistry , alkyl , alternative medicine , receptor , physics , electrode , pathology , quantum mechanics , nuclear physics
A series of five Re(pyNHC‐aryl)(CO) 3 X complexes varying the “X” ligand where pyNHC is a pyridyl N‐heterocyclic carbene have been synthesized and characterized through NMR, UV/Vis absorption spectroscopy, IR, mass spectrometry, time‐correlated single photon counting, computational analysis, and cyclic voltammetry. The photocatalytic reduction of CO 2 to CO in the presence of a sacrificial electron donor with these complexes is evaluated using a simulated solar spectrum (AM 1.5G). Comparison of Br and CH 3 CN as the “X” ligand shows the same photocatalytic activity (both 32 TON). The use of Cl, NCS and P(OEt) 3 “X” ligands all led to diminished reactivity with as little as 2 TON for the P(OEt) 3 complex. These results were rationalized through computational analysis of “X” dissociation and excited‐state lifetime measurements. These results highlight the importance of the “X” ligand selection on catalysis with Re‐pyNHC complexes.