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)
Malberg J, Lupton E, Schnoeckelborg EM, De Bruin B, Sutter J, Meyer K, Hartl F, Wolf R (2013)
Publication Status: Published
Publication Type: Journal article, Letter
Publication year: 2013
Journal
Publisher: American Chemical Society
Book Volume: 32
Pages Range: 6040-6052
Journal Issue: 20
DOI: 10.1021/om4005862
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.
Authors with CRIS profile
Jörg Sutter
Lehrstuhl für Anorganische und Allgemeine Chemie
Karsten Meyer
Lehrstuhl für Anorganische und Allgemeine Chemie
Involved external institutions
Universität Regensburg
Germany (DE)
University of Amsterdam
Netherlands (NL)
University of Reading
United Kingdom (GB)
Germany (DE)
University of Amsterdam
Netherlands (NL)
University of Reading
United Kingdom (GB)
How to cite
APA:
Malberg, J., Lupton, E., Schnoeckelborg, E.-M., De Bruin, B., Sutter, J., Meyer, K.,... Wolf, R. (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), 6040-6052. https://doi.org/10.1021/om4005862
MLA:
Malberg, Jennifer, et al. "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 (2013): 6040-6052.
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