"Hummingbird" behaviour of N-heterocyclic carbenes stabilises out-of-plane bonding of AuCl and CuCl units.

An N-heterocyclic carbene substituted by two expanded 9-ethyl-9-fluorenyl groups was shown to bind an AuCl unit in an unusual manner, namely with the AuX rod sitting out of the plane defined by the heterocyclic carbene unit. As shown by X-ray studies and DFT calculations, the observed large pitch angle (21°) arises from an easy displacement of the gold(I) atom away from the carbene lone-pair axis, combined with the stabilisation provided by weak CH⋅⋅⋅Au interactions involving aliphatic and aromatic H atoms of the NHC wingtips. Weak, intermolecular Cl⋅⋅⋅H bonds are likely to cooperate with the H⋅⋅⋅Au interactions to stabilise the out-of-plane conformation. A general belief until now was that tilt angles in NHC complexes arise mainly from steric effects within the first coordination sphere.