Diborane, Diborene and M(I)‐η2‐Diborene Complexes Stabilized by Bicyclic (Alkyl)(Amino)Carbene (M=Cu and Ag)

BICAAC (bicyclic (alkyl)(amino)carbene) as ambiphilic carbene has been utilized to prepare stable neutral tetrahydrodiborane [BICAAC → ${\to }$ (H2)B−B(H2) ← ${\leftarrow }$ BICAAC] and dihydrodiborene [BICAAC→(H)B=B(H) ← ${\leftarrow }$ BICAAC] compounds. The Lewis base stabilized dihydrodiborene is isoelectronic and isolobal to conventional olefins and therefore offers the possibility to explore the formation of π‐complexes with transition metals. Reaction of the diborene with coinage metal salts (CuCl, AgBr and CuI) leads to the formation of π‐diborene metal complexes via η2 side‐on coordination. These are first examples of dihydrodiborene coinage metal complexes. Interestingly, coordination of two CuCl units to the diborene has been observed for the first time with a considerable lengthening of >B=B< and B - ${-}$ CBICAAC bonds manifesting the key role of the BICAAC combined with small steric requirements of hydride substituents in stabilizing these complexes. The energy decomposition analysis (EDA) calculations reveal the interaction between the diborene and Cu(I)/Ag(I) is mainly electrostatic in nature. The ambiphilic property of bicyclic (alkyl)(amino)carbene (BICAAC) has been utilized for stabilizing dihydrodiborene, which shares isoelectronic and isolobal characteristics with conventional olefins. This diborene presents an opportunity to investigate the formation of η2‐complexes with transition metal salts such as CuCl, AgBr and CuI. Notably, these represent the first examples of transition metal complexes involving dihydrodiborene. Furthermore, the coordination of two CuCl molecules to a diborene has been observed for the first time.