Tuning the Oxidation Level, the Spin State, and the Degree of Electron Delocalization in Homo- and Heteroleptic Bis(α-diimine)iron Complexes.
The four-coordinate heteroleptic complex [Fe (pda)(Fdad)] (1) and its homoleptic analogue [Fe(dad)] (2), where pda is the closed-shell ligand N,N'-bis(pentafluorophenyl)-o-phenylenedia- mide(2-) and dad is the singly reduced N,N'-bis(pentafluorophenyl)-2,3-dimethyl-1,4-diazabutadiene π-radical anion...
| Publicado en: | Journal of the American Chemical Society Vol. 131; no. 3; pp. 1208 - 1222 |
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| Autores principales: | , , , |
| Formato: | Artículo |
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American Chemical Society
1/28/2009
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=36570858&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 36570858 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 1/28/2009 vid: 131 iid: 3 pid: 997 pub: American Chemical Society artinfo: ui: 36570858 10.1021/ja808149k ppf: 1208 ppct: 14 formats: tig: atl: Tuning the Oxidation Level, the Spin State, and the Degree of Electron Delocalization in Homo- and Heteroleptic Bis(α-diimine)iron Complexes. aug: au: Khusniyarov, Marat M. Weyhermuller, Thomas Bill, Eckhard Wieghardt, Karl affil: Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr, Germany. su: Oxidation Spectrum analysis X-ray crystallography Density functionals Ligands (Chemistry) sug: subj: Oxidation Spectrum analysis X-ray crystallography Density functionals Ligands (Chemistry) ab: The four-coordinate heteroleptic complex [Fe (pda)(Fdad)] (1) and its homoleptic analogue [Fe(dad)] (2), where pda is the closed-shell ligand N,N'-bis(pentafluorophenyl)-o-phenylenedia- mide(2-) and dad is the singly reduced N,N'-bis(pentafluorophenyl)-2,3-dimethyl-1,4-diazabutadiene π-radical anion, have been synthesized. X-ray crystallographic studies reveal a twisted tetrahedral geometry of the FeN coordination polyhedron in both 1 and 2. The electronic structures of 1 and 2 were probed by magnetic susceptibility measurements, Fe MOssbauer and electronic spectroscopy, and density functional theory (DFT) calculations. In spite of their similar geometries and a common triplet ground state (S = 1), the electronic structures of 1, 2, and the previously reported homoleptic analogue [Fe(pda)(pda)] (3), where pda is a one-electron-oxidized form of pda, differ. The electronic structure of 2 consists of two dad radicals coupled antiferromagnetically to a high-spin Fe center, whereas in 3, only one pda radical is coupled antiferromagnetically to an intermediate-spin Fe ion. This ligand mixed-valent species exhibits class-Ill behavior. Heteroleptic 1 contains a single dad radical coupled antiferromagnetically to an intermediate-spin F center but behaves as a class-Il ligand mixed-valent species. The observed diversity in the electronic structures of 1-3 is ascribed to the difference in the redox potentials of the ligands. Analysis of reduced orbital charges and spin densities obtained from DFT calculations also suggests that the electronic structures of 1-3 are best described as either a high-spin Fe ion coordinated to two radical monoanions (2) or as an intermediate-spin Fe ion coordinated to one radical monoanion and one closed- shell dianion (1, 3). pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2009 holdings: @attributes: islocal: N |
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