Matthew V Vollmer1, Charles W Machan2, Melissa L Clark2, William E Antholine3, Jay Agarwal4, Henry F Schaefer4, Clifford P Kubiak2, Justin R Walensky1. 1. Department of Chemistry, University of Missouri, Columbia, Missouri 65211, United States. 2. Department of Chemistry & Biochemistry, University of California, San Diego, California 92093, United States. 3. Department of Biophysics, Medical College of Wisconsin, Milwaukee, Wisconsin 53226, United States. 4. Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States.
Abstract
The synthesis and characterization of new Mn(I)- and Re(I)-centered organometallic complexes fashioned with 1,4-diazabutadiene (DAB) ligands is reported. Ten compounds of the type fac-(α-diimine)M(CO)3Br (M = Mn, Re) were obtained in moderate to excellent yield (35-80%) and high purity from the coordination of the five ligands with M(CO)5Br in refluxing ethanol. Despite the electronic similarity of DAB to 2,2'-bipyridyl, the complexes described herein were poor mediators of electrochemical CO2 conversion to CO, but provide insight into the role of redox-active ligands in catalysis. Additional characterization of the one-electron reduced rhenium compounds, relevant intermediates in CO2 reduction, by EPR and single-crystal X-ray analysis is described.
The synthesis and characterization of new Mn(I)- and n class="Chemical">Re(I)-centered organometallic complexes fashioned with 1,4-diazabutadiene (DAB) ligands is reported. Ten compounds of the type fac-(α-diimine)M(CO)3Br (M = Mn, Re) were obtained in moderate to excellent yield (35-80%) and high purity from the coordination of the five ligands with M(CO)5Br in refluxing ethanol. Despite the electronic similarity of DAB to 2,2'-bipyridyl, the complexes described herein were poor mediators of electrochemical CO2conversion to CO, but provide insight into the role of redox-active ligands in catalysis. Additional characterization of the one-electron reduced rhenium compounds, relevant intermediates in CO2 reduction, by EPR and single-crystal X-ray analysis is described.
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