Can a Wanzlick-like equilibrium exist between dicoordinate borylenes and diborenes?

Boron chemistry has experienced tremendous progress in the last few decades, resulting in the isolation of a variety of compounds with remarkable electronic structures and properties. Some examples are the singly Lewis-base-stabilised borylenes, wherein boron has a formal oxidation state of +I, and their dimers featuring a boron-boron double bond, namely diborenes. However, no evidence of a Wanzlick-type equilibrium between borylenes and diborenes, which would open a valuable route to the latter compounds, has been found. In this work, we combine DFT, coupled-cluster, multireference methods, and natural bond orbital/natural resonance theory analyses to investigate the electronic, structural, and kinetic factors controlling the reactivity of the transient CAAC-stabilised cyanoborylene, which spontaneously cyclotetramerises into a butterfly-type, twelve-membered (BCN)₄ ring, and the reasons why its dimerisation through the boron atoms is hampered. The computations are also extended to the NHC-stabilised borylene counterparts. We reveal that the borylene ground state multiplicity dictates the preference for self-stabilising cyclooligomerisation over boron-boron dimerisation. Our comparison between NHC- vs. CAAC-stabilised borylenes provides a convincing rationale for why the reduction of the former always gives diborenes while a range of other products is found for the latter. Our findings provide a theoretical background for the rational design of base-stabilised borylenes, which could pave the way for novel synthetic routes to diborenes or alternatively non-dimerising systems for small-molecule activation.