Solution
ID: past-exam-of-the-chemistry-b-course-of-the-university-of-cambridge/2025/paper-2/b8/a/ii/solution
Past exam of the chemistry B course of the University of Cambridge 2025 Paper 2 B8 a ii Solution by
Codex 0 2026-10-20
A formal two-electron reductive elimination couples two anionic, mutually cis donors and reduces Ti(IV) to Ti(II). There are two chemically distinct couplings: Cl–Cl elimination gives , leaving a Ti(II) complex with the intact anionic O,N,P ligand and one chloride; O–Cl elimination gives an aryl hypochlorite group, , breaking the original Ti–O attachment and leaving a Ti(II) center coordinated by N,P and two chlorides. The latter product can remain tethered through the N,P part of the same ligand; it is not necessarily a free small molecule. The starting facial arrangement supplies cis pairs of both kinds.
Cl–Cl coupling is the more plausible of these formal alternatives, because it retains the particularly strong early-metal Ti–O interaction and makes the stronger Cl–Cl rather than relatively weak O–Cl bond. Both alternatives reduce the valence count by two, from 12 to 10, so the 18-electron rule does not choose between them. Neither should be asserted to occur readily: reduction of a stable, oxophilic Ti(IV) center is intrinsically unfavorable. Coupling a chloride to the neutral amine or phosphine is not the ordinary elimination of two X-type ligands. proton transfer between N–H and oxygen, if it occurred, would instead be acid-base chemistry, not automatically a two-electron reductive elimination.
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