Abstract
Isotropic electron paramagnetic resonance spectra of square pyramidal Co(CO)3L2 and trigonal bipyramidal Co(CO)2PPh3L2 in toluene, dichloromethane and THF solutions show small 59Co hyperfine couplings and g-values close to the free-electron value, suggesting that the complexes are best described as CoI coordinated by an L2 radical anion. The frozen solution spectrum of Co(CO)3L2 in toluene or THF shows anisotropic 59Co coupling corresponding to a 3d spin density of 0.016. In both cases, the 59Co and 31P hyperfine couplings are strongly temperature dependent. Complex linewidth effects in the spectra of the PPh3 derivative suggest a pseudorotation process which interconverts trigonal bipyramidal and square pyramidal conformations, averaging the couplings of the 31P nuclei of the L2 ligand. Analysis of spectra of CH2Cl2 solutions leads to activation parameters for pseudorotation: ΔH‡= 14 kJ mol–1, ΔS‡=–66 J mol–1 K–1.
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