Malberg, Jennifer and Lupton, Elizabeth and Schnoeckelborg, Eva-Maria and de Bruin, Bas and Sutter, Joerg and Meyer, Karsten and Hartl, Frantisek and Wolf, Robert (2013) Synthesis and Electronic Structure of Dissymmetrical, Naphthalene-Bridged Sandwich Complexes [Cp ' Fe(mu-C10H8)MCp*](x) (x=0,+1; M = Fe, Ru; Cp ' = eta(5)-C5H2-1,2,4-tBu(3); Cp* = eta(5)-C5Me5). ORGANOMETALLICS, 32 (20). pp. 6040-6052. ISSN 0276-7333, 1520-6041
Full text not available from this repository. (Request a copy)Abstract
The dissymmetrical naphthalene-bridged complexes [Cp'Fe(mu-C10H8)FeCp*] (3; Cp* = eta(5)-C5Me5, Cp' = eta(5)-C5H2-1,2,4-tBu(3)) and [Cp'Fe(mu-C10H8)RuCp*] (4) were synthesized via a one-pot procedure from FeCl2(thf)(1.5), Cp'K, KC10H8, and [Cp*FeCl(tmeda)] (tmeda = N,N,N',N'-tetramethylethylenediamine) or [Cp*RuCl](4), respectively. The symmetrically substituted iron ruthenium complex [Cp*Fe(mu-C10H8)RuCp*] (5) bearing two Cp* ligands was prepared as a reference compound. Compounds 3-5 are diamagnetic and display similar molecular structures, where the metal atoms are coordinated to opposite sides of the bridging naphthalene molecule. Cyclic voltammetry and UV/vis spectroelectrochemistry studies revealed that neutral 3-5 can be oxidized to monocations 3(+)-5(+) and dications 3(2+)-5(2+). The chemical oxidation of 3 and 4 with [Cp2Fe]PF6 afforded the paramagnetic hexafluorophosphate salts [Cp'Fe(mu-C10H8)FeCp*]PF6 ([3]PF6) and [Cp'Fe(mu-C10H8)RuCp*]PF6 ([4]PF6), which were characterized by various spectroscopic techniques, including EPR and Fe-57 Mossbauer spectroscopy. The molecular structure of [4]PF6 was determined by X-ray crystallography. DFT calculations support the structural and spectroscopic data and determine the compositions of frontier molecular orbitals in the investigated complexes. The effects of substituting Cp* with Cp' and Fe with Ru on the electronic structures and the structural and spectroscopic properties are analyzed.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | UNSATURATED HYDROCARBON BRIDGES; DENSITY-FUNCTIONAL CALCULATIONS; ORDER REGULAR APPROXIMATION; MIXED-VALENCE CHEMISTRY; TRIPLE ZETA VALENCE; GAUSSIAN-BASIS SETS; SOLID-STATE; ORGANOMETALLIC COMPLEXES; POLYAROMATIC MOLECULES; CORRELATION-ENERGY; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 27 Mar 2020 08:47 |
| Last Modified: | 27 Mar 2020 08:47 |
| URI: | https://pred.uni-regensburg.de/id/eprint/15827 |
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