{"4d706dcb4a19a406cc9383fec48be027huebleriac":{"DOI":"10.1021/ja025829n","ISBN":"","ISSN":"0002-7863","URL":"","abstract":"The dinuclear radical anion complexes (μ-L)[Re(CO)3Cl]2.bul.-, L = 2,2'-azobispyridine (abpy) and 2,2'-azobis(5-chloropyrimidine) (abcp), were studied by EPR at 9.5, 94, 230, and 285 GHz (abpy complex) and at 9.5 and 285 GHz (abcp complex).  Whereas the X-band measurements yielded only the isotropic metal hyperfine coupling of the 185,187Re isotopes, the high-frequency EPR expts. in glassy frozen CH2Cl2/toluene soln. revealed the g components.  Both the a(185,187Re) value and the g anisotropy, g1 - g3, are larger for the abcp complex, which contains the better p-accepting bridging ligand.  Confirmation for this comes also from IR and UV/visible spectroscopy of the new (μ-abcp)[Re(CO)3Cl]2o/.bul.-/2- redox system.  The g values are reproduced reasonably well by d. functional calcns. which confirm higher metal participation at the singly occupied MO and therefore larger contributions from the metal atoms to the g anisotropy in abcp systems compared to abpy complexes.  Addnl. calcns. for systems (μ-abcp)[M(CO)3X]2.bul.- (M = Tc or Re and X = Cl, and X = F, Cl, or Br with M = Re) provided further insight into the relation between spin d. distribution and g anisotropy. [on SciFinder(R)]","annote":"","author":[{"family":"Frantz","given":"Stephanie"},{"family":"Hartmann","given":"Heiko"},{"family":"Doslik","given":"Natasa"},{"family":"Wanner","given":"Matthias"},{"family":"Kaim","given":"Wolfgang"},{"family":"Kuemmerer","given":"Hans-Juergen"},{"family":"Denninger","given":"Gert"},{"family":"Barra","given":"Anne-Laure"},{"family":"Duboc-Toia","given":"Carole"},{"family":"Fiedler","given":"Jan"},{"family":"Ciofini","given":"Ilaria"},{"family":"Urban","given":"Christian"},{"family":"Kaupp","given":"Martin."}],"citation-label":"Frantz.2002","collection-editor":[],"collection-title":"","container-author":[],"container-title":"Journal of the American Chemical Society","documents":[],"edition":"","editor":[],"event-date":{"date-parts":[["2002"]],"literal":"2002"},"event-place":"","id":"4d706dcb4a19a406cc9383fec48be027huebleriac","interhash":"171b2796c8cc6986ef821d23de1ae9a2","intrahash":"4d706dcb4a19a406cc9383fec48be027","issue":"35","issued":{"date-parts":[["2002"]],"literal":"2002"},"keyword":"EPR complex complex;UV complex;spin density g multifrequency organo persistent radical rhenium spectra tensor visible","misc":{"issn":"0002-7863","doi":"10.1021/ja025829n"},"note":"","number":"35","number-of-pages":"8","page":"10563--10571","page-first":"10563","publisher":"","publisher-place":"","status":"","title":"Multifrequency EPR Study and Density Functional g-Tensor Calculations of Persistent Organorhenium Radical Complexes","type":"article-journal","username":"huebleriac","version":"","volume":"124"},"4d706dcb4a19a406cc9383fec48be027b_schwederski":{"DOI":"10.1021/ja025829n","ISBN":"","ISSN":"0002-7863","URL":"","abstract":"The dinuclear radical anion complexes (μ-L)[Re(CO)3Cl]2.bul.-, L = 2,2'-azobispyridine (abpy) and 2,2'-azobis(5-chloropyrimidine) (abcp), were studied by EPR at 9.5, 94, 230, and 285 GHz (abpy complex) and at 9.5 and 285 GHz (abcp complex).  Whereas the X-band measurements yielded only the isotropic metal hyperfine coupling of the 185,187Re isotopes, the high-frequency EPR expts. in glassy frozen CH2Cl2/toluene soln. revealed the g components.  Both the a(185,187Re) value and the g anisotropy, g1 - g3, are larger for the abcp complex, which contains the better p-accepting bridging ligand.  Confirmation for this comes also from IR and UV/visible spectroscopy of the new (μ-abcp)[Re(CO)3Cl]2o/.bul.-/2- redox system.  The g values are reproduced reasonably well by d. functional calcns. which confirm higher metal participation at the singly occupied MO and therefore larger contributions from the metal atoms to the g anisotropy in abcp systems compared to abpy complexes.  Addnl. calcns. for systems (μ-abcp)[M(CO)3X]2.bul.- (M = Tc or Re and X = Cl, and X = F, Cl, or Br with M = Re) provided further insight into the relation between spin d. distribution and g anisotropy. [on SciFinder(R)]","annote":"","author":[{"family":"Frantz","given":"Stephanie"},{"family":"Hartmann","given":"Heiko"},{"family":"Doslik","given":"Natasa"},{"family":"Wanner","given":"Matthias"},{"family":"Kaim","given":"Wolfgang"},{"family":"Kuemmerer","given":"Hans-Juergen"},{"family":"Denninger","given":"Gert"},{"family":"Barra","given":"Anne-Laure"},{"family":"Duboc-Toia","given":"Carole"},{"family":"Fiedler","given":"Jan"},{"family":"Ciofini","given":"Ilaria"},{"family":"Urban","given":"Christian"},{"family":"Kaupp","given":"Martin."}],"citation-label":"Frantz.2002","collection-editor":[],"collection-title":"","container-author":[],"container-title":"Journal of the American Chemical Society","documents":[],"edition":"","editor":[],"event-date":{"date-parts":[["2002"]],"literal":"2002"},"event-place":"","id":"4d706dcb4a19a406cc9383fec48be027b_schwederski","interhash":"171b2796c8cc6986ef821d23de1ae9a2","intrahash":"4d706dcb4a19a406cc9383fec48be027","issue":"35","issued":{"date-parts":[["2002"]],"literal":"2002"},"keyword":"EPR complex complex;UV complex;spin density g multifrequency organo persistent radical rhenium spectra tensor visible","misc":{"issn":"0002-7863","doi":"10.1021/ja025829n"},"note":"","number":"35","number-of-pages":"8","page":"10563--10571","page-first":"10563","publisher":"","publisher-place":"","status":"","title":"Multifrequency EPR Study and Density Functional g-Tensor Calculations of Persistent Organorhenium Radical Complexes","type":"article-journal","username":"b_schwederski","version":"","volume":"124"}}