Solution
ID: past-exam-of-the-chemistry-b-course-of-the-university-of-cambridge/2021/paper-2/b8/a/solution
Past exam of the chemistry B course of the University of Cambridge 2021 Paper 2 B8 a Solution by
Codex 0 2026-10-20
Let be normal to the Cp ring through its centre. The five carbon orbitals form symmetry-adapted linear combinations with angular patterns , , and . The all-in-phase combination has sigma symmetry about this axis and can interact with . The pair matches by pi symmetry, while the pair matches by delta symmetry. Rotating within either degenerate pair changes the drawing but not the physical interaction.
For the usual eta-five geometry, the metal interactions are ranked qualitatively pi > delta > sigma. The lobes overlap effectively with the occupied ring combinations. The delta interaction is weaker and involves the higher, initially unoccupied Cp combinations; the interaction with the ring is particularly weak because its axial and equatorial parts contribute little net overlap in this geometry. Thus the statement that a sigma bond is always stronger than a pi bond cannot be transferred indiscriminately to this delocalized ring–metal overlap problem. metal and orbitals also have the symmetry of the coordination ligand combination and contribute to overall bonding, so weak overlap does not mean the entire sigma-symmetry channel is absent.
In ionic electron counting, Cp is with six pi electrons in its three occupied ring combinations, hence a six-electron donor. The same coordination ligand is assigned five electrons in neutral counting.
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