Solution

ID: past-exam-of-the-chemistry-course-of-the-year-3-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-1/1/a/solution

is nido; and are arachno. The initial hydride removes an acidic bridging hydrogen as a proton, releasing and retaining the potassium counterion. Addition of one unit expands the boron framework; final protonation supplies the neutral hexaborane and KCl. These assignments conserve all the atoms in the displayed sequence, without inserting an unshown dehydrogenation step.
For , take one terminal B–H bond per vertex and remove its electrons from the valence total. The skeletal electron count is . Thus
Wade's rules assign , and pairs to closo, nido and arachno frameworks respectively. A derives from a six-vertex closo octahedron by removal of one vertex, giving a square-pyramidal boron skeleton. B and C have six-vertex open frameworks formally derived from an eight-vertex closo polyhedron by removing two vertices. Their additional hydrogens are distributed over bridging and other open-face positions; counting every hydrogen as an independent terminal B–H vertex would give the wrong classification.
The arachno assignment of has specific theoretical and NMR support. It should not be replaced by a permanently localized, unrearranged picture: the corresponding symmetric adduct participates in fluxional rearrangement rather than being the lowest-energy structure.[ref]
Figure 1.
Original skeletal-electron accounting for the nido-to-arachno borane sequence
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