title: Multifrequency EPR studies of [Cu(1.5)Cu(1.5)](+) for Cu2(mu-NR2)2 and Cu2(mu-PR2)2 diamond cores.
abstract: Multifrequency electron paramagnetic resonance (EPR) spectroscopy is used to explore the electronic structures of a series of dicopper complexes of the type {(LXL)Cu}(2)(+). These complexes contain two four-coordinate copper centers of highly distorted tetrahedral geometries linked by two [LXL](-) ligands featuring bridging amido or phosphido ligands and associated thioether or phosphine chelate donors. Specific chelating [LXL](-) ligands examined in this study include bis(2-tert-butylsulfanylphenyl)amide (SNS), bis(2-di-iso-butylphosphinophenyl)amide (PNP), and bis(2-di-iso-propylphosphinophenyl)phosphide (PPP). To better map the electronic coupling to copper, nitrogen, and phosphorus in these complexes, X-, S-, and Q-band EPR spectra have been obtained for each complex. The resulting EPR parameters implied by computer simulation are unusual for typical dicopper complexes and are largely consistent with previously published X-ray absorption spectroscopy and density functional theory data, where a highly covalent {Cu(2)(mu-XR(2))(2)}(+) diamond core has been assigned in which removal of an electron from the neutral {Cu(2)(mu-XR(2))(2)} can be viewed as ligand-centered to a substantial degree. To our knowledge, this is the first family of dicopper diamond core model complexes for which the compendium of X-, S-, and Q-band EPR spectra have been collected for comparison to Cu(A).
authors: Department of Chemistry, Massachusetts Institute of Technology, Cambridge Massachusetts 02139, USA.
authors: Neal P
authors: NP
authors: Mankad
authors: Seth B
authors: SB
authors: Harkins
authors: William E
authors: WE
authors: Antholine
authors: Jonas C
authors: JC
authors: Peters
mesh_terms: D002412:Cations / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D006576:Heterocyclic Compounds, 4 or More Rings / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation
chemical_list: D002412:Cations; D006576:Heterocyclic Compounds, 4 or More Rings; D003300:Copper