Boron mono- and di-cations featuring a nucleophilic N-heterocyclic olefin and the pentamethylcyclopentadienyl substituent have been prepared and structurally characterized. Experimental and theoretical investigations show that [η(5)-Cp*B-NHO](2+) is considerably more Lewis acidic than [η(5)-Cp*B-IMes](2+) due to the steric congestion imposed by the bent geometry of NHO around the central boron atom.