About nitrito- and nitropentaamminecobalt(III) chloride.

As can be seen there are only minor differences in the written procedures for the preparation of the
two linkage isomers. In both cases the reaction is represented by

[Co(NH3)5Cl]2+ + NO2- → [Co(NH3)5NO2]2+ + Cl-

The mechanism of reaction will in both cases go through the o-bonded isomer (the nitrito-isomer),
which is unstable and gradually converts to the N-bonded isomer (the nitro-isomer) in an
equilibration process. Dependent on the conditions the equilibrated mixture will consist of, say 5-
10% of the nitrite-isomer, because the equilibrium in aqueous acid solution

[Co(NH3)5ONO]2+ ↔ [Co(NH3)5NO2]2+
lies very much to the right.
The equilibration in the solid phase in the dark is very slow at room temperature, while in acid
solution without the exclusion of light it is a question of hours.
Absorption spectra in the visible and UV spectral region of solutions are difficult and uncertain
because the equilibration is catalysed by light and acid, so other evidence of the identity and purity
of the two isomers has to be given.
IR-spectroscopy (4000-400 cm-1) is suited for that purpose because the Co-O-N-O and the Co-N-O
fragments have different vibrational patterns.

KBr-tablets with 1-2% of the dry compound are suited for the purpose

Below is given the most important resonance-frequencies in cm-1

intensities are given qualitatively by
• vs: very strong
• s: strong
• m: medium
• w: weak
band widths are only given in case of broad bands and not in the case of sharp lines
• (vb) : very broad
• (b) : broad
[Co(NH3)5NO2]Cl2 [Co(NH3)5ONO]Cl2
~3200 vs (vb) ~3200 vs (vb)
~1600 m (vb) ~1600 m (vb)
- 1450 s
1425 vs -
1345 w -
1315 vs 1315 vs
1220 w 1220 w
- 1060 vs
840 s (b) 840 s (b)
820 s -
590 m -
495 w -
430 w (b) -