When, Where and Why Boron Prefers Boron to Nitrogen

Abstract

AbstractBoron is the archetypal Lewis acid, and therefore it is only natural that it prefers to bind nitrogen, its usual Lewis base counterpart. To challenge this assumption, we present a computationally designed bicyclopentane molecule akin to [1.1.1]propellane, but with pyramidal B and N inner atoms bonded by an “inverted” dative bond. Unexpectedly, the dimer of this system prefers to interact via an atypical boron‐boron bond over the supposedly obvious boron‐nitrogen bond. A molecular orbital analysis shows that the boron in this peculiar entity acts both as an electron donor and an electron acceptor, making the dimerization an amphoteric‐amphoteric interaction process.