title: Correlation of the electronic and geometric structures in mononuclear copper(II) superoxide complexes.
abstract: The geometry of mononuclear copper(II) superoxide complexes has been shown to determine their ground state where side-on bonding leads to a singlet ground state and end-on complexes have triplet ground states. In an apparent contrast to this trend, the recently synthesized (HIPT3tren)Cu(II)O2(•-) (1) was proposed to have an end-on geometry and a singlet ground state. However, reexamination of 1 with resonance Raman, magnetic circular dichroism, and (2)H NMR spectroscopies indicate that 1 is, in fact, an end-on superoxide species with a triplet ground state that results from the single Cu(II)O2(•-) bonding interaction being weaker than the spin-pairing energy.
authors.affiliation: Department of Chemistry, Stanford University , Stanford, California 94305, United States.
authors.forename: Jake W
authors.initials: JW
authors.lastname: Ginsbach
authors.forename: Ryan L
authors.initials: RL
authors.lastname: Peterson
authors.forename: Ryan E
authors.initials: RE
authors.lastname: Cowley
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Karlin
authors.forename: Edward I
authors.initials: EI
authors.lastname: Solomon
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D004583:Electrons; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D013481:Superoxides / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D013481:Superoxides; D003300:Copper