Solution

ID: past-exam-of-the-chemistry-b-course-of-the-university-of-cambridge/2024/paper-2/b9/b/i/solution

The methyl nucleophile attacks an electrophilic ring boron. That boron becomes tetrahedral, bearing its original methyl, the incoming methyl, and its two ring nitrogen neighbors. This interrupts its p-orbital participation, so the metal attaches to the remaining five-atom conjugated segment. is the anionic heptamethylated-ring Cr(CO) complex, paired formally with ; solvent ligation and ion pairing at magnesium are not specified by the spectrum. The original connectivity, with the attacked boron labeled , is shown in the first panel below.
Figure 1.
Structures inferred from nucleophilic addition, Lewis-acid binding and B–Br oxidative addition
. Details.
There are seven methyl groups. The two attached to tetrahedral are inequivalent because the chromium-bound face distinguishes their environments: one signal of relative integral one for each. The other two B–Me groups are equivalent to one another, giving a signal of integral two. The two N–Me groups adjacent to form another equivalent pair, while the N–Me opposite is unique. The predicted methyl-group multiplicities are therefore , the same unordered set as the observed ratio. Multiplying by three gives proton integrals totaling 21. This assignment assumes no fast process interchanging the two methyl environments.
The six-electron neutral ring donor has become an anionic six-electron donor, so Cr(0) retains an 18-electron count: . This borazine dearomatization explains both the changed hapticity and the extra methyl without requiring attack at chromium or loss of a carbonyl.

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