Solution
ID: past-exam-of-the-chemistry-b-course-of-the-university-of-cambridge/2025/paper-2/b6/a/solution
Past exam of the chemistry B course of the University of Cambridge 2025 Paper 2 B6 a Solution by
Codex 0 2026-10-20
The nitrite ion is an ambidentate ligand: its Lewis structures leave donor lone pairs on both nitrogen and oxygen. In the N-bound mode, , the nitrogen lone pair makes a sigma bond to the metal, while a suitable unoccupied nitrite molecular orbital can accept metal electron density by pi backbonding. Thus N-bound nitro is a sigma donor and pi acceptor. The nitrite group remains bent at nitrogen; N coordination does not make it a linear nitrosyl.
In the O-bound mode, , an oxygen lone pair makes the metal–oxygen sigma bond. A second occupied oxygen orbital can donate sideways into an available metal orbital: O-bound nitrito is a sigma and pi donor, rather than the strong pi acceptor of the N-bound description. oxygen's greater electronegativity lowers its donor orbital energies, but the occupied oxygen orbitals still explain its pi-donor classification. Actual mixing depends on metal oxidation state and geometry.
A further possibility is bidentate coordination, , with both oxygen atoms attached to one metal. Each attachment has oxygen-to-metal sigma donation; additional pi donation depends on orbital alignment. nitrite can also be a bridging ligand between metals. Neither alternative should be confused with linkage isomerism, which specifically compares attachment through different atoms at the same binding site.
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