Spectroscopic Oxidation States
Although formal oxidation numbers can be helpful for classifying compounds, they are unmeasurable and their physical meaning can be ambiguous. Formal oxidation numbers require particular caution for molecules where the bonding is covalent, since the formal oxidation numbers require the heterolytic removal of ligands, which essentially denies covalency. Spectroscopic oxidation states, as defined by Jorgenson and reiterated by Wieghardt, are measurables that are bench-marked using spectroscopic and crystallographic data.
Oxidation state can also have effect on spectroscopic studies of compounds. In infrared spectroscopy of metal carbonyls this effect is illustrated by using spectroscopic studies on metals from oxidation states of −2 to +2.
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