Multifrequency EPR Studies of [Cu^(1.5)Cu^(1.5)]+ for Cu_2(μ-NR_2)_2 and Cu_2(μ-PR_2)_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(μ-XR_2)_2}^+ diamond core has been assigned in which removal of an electron from the neutral {Cu_2(μ-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.
Additional Information
Copyright © 2009 American Chemical Society. Received September 30, 2008. Publication Date (Web): July 2, 2009. J.C.P. acknowledges support from the NSF (GOALI). N.P.M. is grateful for an NSF graduate fellowship. W.E.A. acknowledges the National Biomedical EPR Center Grant EB001980 from NIH. The authors are grateful to a reviewer concerning the EPR simulations. Supporting Information: Crystallographic data (CIF) and supporting EPR spectra are available free of charge via the Internet at http://pubs.acs.org.Attached Files
Supplemental Material - Mankadic801864z_si_001.cif
Supplemental Material - Mankadic801864z_si_002.pdf
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Additional details
- Eprint ID
- 15534
- Resolver ID
- CaltechAUTHORS:20090901-145018265
- NSF
- NIH
- EB001980
- Created
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2009-09-14Created from EPrint's datestamp field
- Updated
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2021-11-08Created from EPrint's last_modified field