Abstract: | A new six‐membered cyclic frustrated phosphane/borane Lewis pair was liberated from its HB(C6F5)2 adduct by treatment with vinylcyclohexane. The system is an active frustrated Lewis pair that undergoes cycloaddition reactions with suitable π reagents and it splits dihydrogen. At room temperature in solution the new compound is a monomer, however, in the crystal and in solution at low temperature it aggregates to a thermodynamically favoured supramolecular macrocyclic cyclooctamer. |