The N-bound isomer is the thermodynamically favored form; heating accelerates access to it. Formation of retains the original metal–oxygen attachment and is a plausible kinetic control outcome. Rearranging that attachment requires overcoming an activation free energy, especially at a substitutionally inert low-spin cobalt(III) center. Raising temperature speeds the linkage isomerization, allowing the more stable N-bound nitro ligand to accumulate. Its stronger ligand field and different covalent bonding help rationalize the stability, but a larger field splitting alone is not a complete calculation of the isomerization Gibbs free energy. The classical crystallographic comparison establishes the different attachments and thermodynamic direction.[ref]
Nitrito-Nitro Linkage Isomerization in the Solid State. 2. A Comparative Study of the Structures of Nitrito- and Nitropentaamminecobalt(III) Dichloride by Ingmar Grenthe and Ellika Nordin. 1979, pp. 1869–1874, structural comparison and solid-state isomerization
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