Premium
Reduction of CO 2 by Pyridine Monoimine Molybdenum Carbonyl Complexes: Cooperative Metal–Ligand Binding of CO 2
Author(s) -
Sieh Daniel,
Lacy David C.,
Peters Jonas C.,
Kubiak Clifford P.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500463
Subject(s) - chemistry , ligand (biochemistry) , adduct , pyridine , cyclic voltammetry , carboxylate , molybdenum , molecule , electrochemistry , stoichiometry , metal , redox , infrared spectroscopy , bipyridine , inorganic chemistry , crystallography , medicinal chemistry , stereochemistry , crystal structure , organic chemistry , biochemistry , receptor , electrode
[( Ar PMI)Mo(CO) 4 ] complexes (PMI=pyridine monoimine; Ar=Ph, 2,6‐di‐ iso ‐propylphenyl) were synthesized and their electrochemical properties were probed with cyclic voltammetry and infrared spectroelectrochemistry (IR‐SEC). The complexes undergo a reduction at more positive potentials than the related [(bipyridine)Mo(CO) 4 ] complex, which is ligand based according to IR‐SEC and DFT data. To probe the reaction product in more detail, stoichiometric chemical reduction and subsequent treatment with CO 2 resulted in the formation of a new product that is assigned as a ligand‐bound carboxylate, [( i Pr 2 Ph PMI)Mo(CO) 3 (CO 2 )] 2− , by NMR spectroscopic methods. The CO 2 adduct [( i Pr 2 Ph PMI)Mo(CO) 3 (CO 2 )] 2− could not be isolated and fully characterized. However, the CC coupling between the CO 2 molecule and the PDI ligand was confirmed by X‐ray crystallographic characterization of one of the decomposition products of [( i Pr 2 Ph PMI)Mo(CO) 3 (CO 2 )] 2− .