Solution

ID: past-exam-of-the-chemistry-b-course-of-the-university-of-cambridge/2022/paper-2/b6/b/v/solution

The Co(III) centre in has : every occupied d subset is orbitally balanced. There is no first-order metal-centred Jahn–Teller driving force in . This does not require all six experimental bond lengths to be equal, since pyridine and dioxolene are different donors.
The Co(II) centre in has . Its two orbitals each contain one electron, so that subset gives no first-order preference. The hole does give a weaker Jahn–Teller instability. To compare tetragonal distortions, take a positive small splitting parameter and retain each subset's orbital energy barycentre. On axial elongation let shift by and by . Five electrons then give
For equal-magnitude compression the shifts reverse, and filling the lower orbital first gives
The two singly occupied orbitals contribute zero net shift in either case. Thus the elementary tetragonal splitting model favours elongation for high-spin , rather than equal electronic stabilization by the two signs. In a strictly sigma-only octahedral molecular orbital model is nonbonding, so this weak effect is absent; it arises when the electrostatic and non-sigma interactions neglected in that diagram are restored. spin-orbit coupling, unequal donors and chelate constraints can modify the actual distortion, so the argument does not establish which experimental Co–donor bonds must lengthen.

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