Dioxolene ligand 2026-10-20
An ortho-dioxygen aromatic framework that can bind through both oxygen atoms in several redox states. The semiquinonate monoanion has a ligand-centred unpaired electron, whereas the catecholate dianion has a filled-shell configuration. non-innocent ligand behaviour means metal oxidation state cannot be inferred from an overall complex charge without specifying the ligand redox state.
The terminal nitrosyls are linear in both proposed electron-precise structures; the formal M–M bond orders are V–V double and Fe–Fe single. Use three-electron terminal linear NO donors, three-electron -NO bridges, and five-electron neutral Cp donors in covalent counting.
For the vanadium dimer the two metal fragments together contain
A metal–metal bond of order adds to each local count, so gives and 18 electrons per V. For an ionic cross-check, Cp is , each linear terminal NO is conventionally NO, and each bridge is represented as NO. Thus
Each V then has electrons.
The iron species is monoanionic, and is a pyrazolate bridge binding through its two nitrogens. This is a four-electron donor overall in ionic counting, or three overall in neutral counting. The carbonyl bridge supplies two electrons overall. The covalent fragment total is consequently
Therefore gives . In the formal NO description,
Each Fe receives electrons. The negative formal oxidation state follows from the chosen nitrosyl assignment and the overall charge; omitting that charge would change the count.
Bent terminal NO ligands would supply fewer neutral-count electrons and demand much higher formal M–M bond orders to attain 18-electron counts. The linear assignments give the ordinary double and single bond solutions. Since NO is a non-innocent ligand, these oxidation states are formal bookkeeping limits, not measured metal charges; actual nitrosyl bending and M–M bond strengths require structural and spectroscopic evidence.[ref]