Past exam of the chemistry B course of the University of Cambridge 2021 Paper 1 B3 d ii Solution 2026-10-20
sulfide first opens one epoxide by backside attack, giving a carbon-bound thiolate and an alkoxide. Using the same numbering, take this first attack at C2: the C2–S bond is down and C3–O remains up.
The attached sulfur still bears a nucleophilic lone pair and negative charge. It attacks C5 of the second epoxide intramolecularly, breaking C5–O and closing a bridge between C2 and C5. Work-up protonates the oxygen anions at C3 and C6. Thus B is 7-thiabicycloheptane-2,5-diol, with both OH groups on the face opposite the sulfur bridge.
Both C–S bonds are formed by inversion at their attacked epoxide carbons. Because the original epoxides are cis, both new C–S bonds point to the same opposite face and one sulfur chemical atom can connect them. The 1,4 bridge gives two five-membered sulfur-containing circuits, unlike the more strained closure between nearby 1,3 positions.
The sulfur therefore replaces two separate external nucleophiles: two epoxides are opened but only one sulfur chemical atom is incorporated. Adding that sulfur and two work-up protons gives , consistent with B.
Past exam of the chemistry B course of the University of Cambridge 2024 Paper 2 B7 a i Solution 2026-10-20
In the ionic assignment, both tetrahedral anions would require Mn(VII), . Such a high oxidation state is strongly oxidizing and is best supported by strong bonding to oxygen. Short Mn–O bonds combine good orbital overlap with oxygen's resistance to further oxidation. This stabilizes permanganate relative to a hypothetical all-sulfide analogue.
sulfide is larger, more polarizable and much easier to oxidize than oxide. An attempted Mn(VII) sulfide would therefore combine an exceptionally oxidizing metal center with reducing ligands: internal redox can reduce manganese while oxidizing sulfur, for example toward S–S-bonded or elemental sulfur products. The larger sulfur donors also provide less favorable short multiple bonding to the small, highly charged manganese center. The oxygen compound supports Mn(VII); the sulfide combination is redox-incompatible. This predicts instability without requiring a specific unprovided decomposition product.