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Some Electron Paramagnetic Resonance Studies of Bis-Cyclopentadienyl Vanadium


Porterfield, William Wendell (1960) Some Electron Paramagnetic Resonance Studies of Bis-Cyclopentadienyl Vanadium. Master's thesis, California Institute of Technology. doi:10.7907/7D95-T093.


Section I: Bis-cyclopentadienyl vanadium was examined by electron paramagnetic resonance (EPR) in dilute benzene solution (1). Vanadium nuclear hyperfine splittings equal to 77 Mc centered at g=2.00 were found, providing experimental evidence that the unpaired electrons occupy orbitals with a very small amount of s character. The orbital ground state is shown to be a singlet. It follows that one of the three unpaired electrons must occupy an orbital of a_(1g) symmetry, the other two orbitals of e_g symmetry, and that the g factor is nearly isotropic. EPR spectra taken of an oxidized solution show hyperfine structure 210 Mc wide at g=1.99, indicating the possible presence of bis-cyclopentadienyl vanadyl, V0(C_5H_5)_2. Section II: EPR spectra were taken of a dilute single crystal of bis-cyclopentadienyl vanadium in ferrocene and the angular dependence of the spectra studied. The spectral lines changed from g^e≃2 at a position with H_0 approximately parallel to the molecular symmetry axis to g^e=3.77 with H_0 perpendicular to this axis, where hν=g^eβH. This angular dependence indicates a zero-field energy level splitting of 47.0 kMc or 1.57 cm^(-1). The bis-cyclopentadienyl vanadium was synthesized by a process originated by Wilkinson (2) but some minor changes were found desirable in product recovery.

Item Type:Thesis (Master's thesis)
Subject Keywords:(Chemistry)
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • McConnell, Harden M.
Thesis Committee:
  • Unknown, Unknown
Defense Date:1 January 1960
Record Number:CaltechTHESIS:04232010-114434337
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:5741
Deposited By: Tony Diaz
Deposited On:28 Jun 2010 22:49
Last Modified:09 Nov 2023 19:41

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