EPR INVESTIGATIONS ON $tris-2,2^{1}$-DIPYRIDYL-COMPLEXES
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Date
1964
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Ohio State University
Abstract
In order to determine experimentally the character of metal-ligand bonds in $tris-2,2^{1}-dipyridyl-complexes$ of transition metals in low oxidation states the electron paramagnetic resonance of the ions $[Cr^{1} dip_{3}]^{+},[V^{0} dip_{3}]$ and $[Ti^{-1} dip_{3}]$- was studied. The positions of the lines in the EPR spectra are given by the spin hamiltonian $\mathcal{H} = g \beta S \cdot H+a S\cdot I+\Sigma_{N} a^{N} S\cdot I^{N}$, where the last term describes the interaction with the nitrogen nuclei of the ligands. Isotropic hyperfine constants and g factors are given. The HFS is mainly accounted for by the exchange polarization of inner core s electrons. Contributions of 4s electrons to the HFS are discussed. The numerical results obtained indicate strong $\sigma-bonding$ between metal 4s and ligand $\Sigma^{+}_{0}$ orbitals which increases in the order $Ti-, V^{0}, Cr^{+}$.
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Author Institution: Mellon Institute