Model
Digital Document
Publisher
Florida Atlantic University
Description
A series of eight-coordinate complexes of molybdenum with 1, 1-dithio
ligands are prepared and characterized by electrochemical and spectroscopic
methods. Cyclic voltammetry in acetonitrile and methylene
chloride solvents reveals reversible metal-based Mo (VI)/Mo(V) and
Mo(V)/Mo(IV) electron transfers. Half-wave potentials are linear
functions of electron withdrawing and donating parameters of the ligand
substituent groups, but do not correlate with charge transfer, vibrational,
or electron paramagnetic resonance spectral data. A linear
relationship does exist between electrochemical half-wave potentials
and Mo 3d and S 2p x-ray photoelectron binding energies. The results
suggest that ligands control half-wave potentials in these complexes
by inductive charge donation to the metal center through bonds not
directly involved in the redox process.
ligands are prepared and characterized by electrochemical and spectroscopic
methods. Cyclic voltammetry in acetonitrile and methylene
chloride solvents reveals reversible metal-based Mo (VI)/Mo(V) and
Mo(V)/Mo(IV) electron transfers. Half-wave potentials are linear
functions of electron withdrawing and donating parameters of the ligand
substituent groups, but do not correlate with charge transfer, vibrational,
or electron paramagnetic resonance spectral data. A linear
relationship does exist between electrochemical half-wave potentials
and Mo 3d and S 2p x-ray photoelectron binding energies. The results
suggest that ligands control half-wave potentials in these complexes
by inductive charge donation to the metal center through bonds not
directly involved in the redox process.
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