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Electronic Structure of the d Bent-metallocene Cp(2)VCl(2): A Photoelectron and Density Functional Study
Matthew A Cranswick1, Nadine E Gruhn, John H Enemark
1Department of Chemistry, The University of Arizona, Tucson, AZ. 85721, USA.
Journal of Organometallic Chemistry
|July 14, 2009
Summary
Photoelectron spectroscopy now accurately measures the binding energy of d electrons in Vanadium dichloride metallocene complexes. This breakthrough provides crucial data for understanding bent metallocene electronic structures.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
- Physical Chemistry
Background:
- Cp(2)VCl(2) is a key bent metallocene complex with a single d electron.
- Previous photoelectron spectroscopy attempts were hindered by molecular decomposition.
Purpose of the Study:
- To accurately measure the binding energy of the d electron in Cp(2)VCl(2) using photoelectron spectroscopy.
- To establish reliable benchmarks for theoretical electronic structure calculations.
Main Methods:
- Utilized advanced photoelectron spectroscopy with improved instrumentation to minimize decomposition.
- Employed spectral subtraction techniques to isolate the Cp(2)VCl(2) signal.
- Performed density functional theory (DFT) calculations for electronic structure analysis.
Main Results:
- Successfully obtained the photoelectron spectrum of Cp(2)VCl(2) by accounting for decomposition products.
- Measured ionization energies serve as accurate benchmarks for theoretical models.
- DFT calculations show excellent agreement with experimental ionization energies for Cp(2)VCl(2).
Conclusions:
- The study overcomes previous experimental limitations in studying Cp(2)VCl(2).
- Experimental data validates theoretical predictions for Cp(2)VCl(2) and related Group V metallocenes.
- Cp(2)VCl(2) exhibits a significantly higher first ionization energy compared to its second- and third-row analogues.
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