title: Synthesis, Spectroscopy, and Electrochemistry of (α-Diimine)M(CO)3Br, M = Mn, Re, Complexes: Ligands Isoelectronic to Bipyridyl Show Differences in CO2Reduction.
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 typefac-(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 CO2reduction, by EPR and single-crystal X-ray analysis is described.
authors.affiliation: Department of Chemistry, University of Missouri, Columbia, Missouri 65211, United States.
authors.forename: Matthew V
authors.initials: MV
authors.lastname: Vollmer
authors.affiliation: Department of Chemistry & Biochemistry, University of California, San Diego, California 92093, United States.
authors.forename: Charles W
authors.initials: CW
authors.lastname: Machan
authors.affiliation: Department of Chemistry & Biochemistry, University of California, San Diego, California 92093, United States.
authors.forename: Melissa L
authors.initials: ML
authors.lastname: Clark
authors.affiliation: Department of Biophysics, Medical College of Wisconsin, Milwaukee, Wisconsin 53226, United States.
authors.forename: William E
authors.initials: WE
authors.lastname: Antholine
authors.affiliation: Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States.
authors.forename: Jay
authors.initials: J
authors.lastname: Agarwal
authors.affiliation: Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States.
authors.forename: Henry F
authors.initials: HF
authors.lastname: Schaefer
authors.affiliation: Department of Chemistry & Biochemistry, University of California, San Diego, California 92093, United States.
authors.forename: Clifford P
authors.initials: CP
authors.lastname: Kubiak
authors.affiliation: Department of Chemistry, University of Missouri, Columbia, Missouri 65211, United States.
authors.forename: Justin R
authors.initials: JR
authors.lastname: Walensky