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Zehnder, Ralph: Polynuclear metallocene complexes incorporating ansa-chromocene and ferrocene units. 2002
Inhalt
Introduction
The Historical Development of Metallocene Complexes of the Early Transition Metals
The Goal of this Work
Ansa-Chromocene(III) Complexes
Polynuclear Ansa-Chromocene(II) isocyanide Complexes
Analytical Methods
NMR-Spectroscopy
IR-Spectroscopy
UV-VIS-NIR Spectroscopy
Cyclic Voltammetry
Magnetic Susceptibility
Association of Magnetic Susceptibility and Magnetic Moment
The Johnson Matthey Magnetic Susceptibility Balance
The Evans NMR Method
Experimentals
General Considerations
Preparation of the Starting Materials
Preparation of all new Polynuclear Ansa-Chromocene isocyanide Complexes
{1,1’-(trans-1,2-diphenylethano) dicyclopentadienyl} (ferrocenylisocyanide) chromium(II) (3)
Bis {1,1’-(trans-1,2-diphenylethano) dicyclopentadienyl} (1,1’-ferrocenyldiisocyanide) chromium(II) (4a)
Bis {1,1’-(tetramethylethano) dicyclopentadienyl} (1,1’-ferrocenyldiisocyanide) chromium(II) (4b)
Bis {1,1’-(tetramethylethano) dicyclopentadienyl} (1,4-phenylene diisocyanide) chromium(II) (5)
Chemical Oxidation of Heteronuclear Complexes
Oxidation of {1,1’-(trans-1,2-diphenylethano) dicyclo-pentadienyl} (ferrocenylisocyanide) chromium(II)
Oxidation of Bis {1,1’-(trans-1,2-diphenylethano) dicyclo-pentadienyl} (1,1’-ferrocenyldiisocyanide) chromium(II)
Determination of the Effective Magnetic Moments
Johnson Matthey Magnetic Susceptibility Balance
Evans Method using the NMR Device
Correction Values
Results
Electrochemistry of Ansa-Chromocene Complexes
Generation of ansa-Chromocene(III) halide Complexes
Synthesis, Physical and Electronic Properties of Hetero nuclear and Homobinuclear Ansa-Chromocene isocyanide Complexes
Synthesis of Ferrocenylisocyanide Derivatives
Synthesis of Ferrocenylisocyanide
Synthesis of Ferrocenyldiisocyanide:
New Synthetic Route to Ansa-Chromocene isocyanides
Synthesis of Neutral Polynuclear Ansa-Chromocene isocyanides
Characterization with NMR- and IR-Spectroscopy
Ligand Exchange with CO
Electrochemistry and X-Ray Single Crystal Structures
UV-VIS Spectroscopy
Chemical Oxidation of Heteronuclear Ansa-Chromocene isocyanide Complexes
Oxidation of 3 and 4a with the Ferrocenylium Cation as well as Benzoquinone
Determination of the Effective Magnetic Moments
Discussion
Conclusions
Future Work
References
Appendix
Magnetic Susceptibility
Determination of the Effective Magnetic Moment using the Evans NMR Method
Determination of the Effective Magnetic Moment using the Evans Matthey Johnson Magnetic Susceptibility Balance
X-Ray Single Crystal Structure Data