AbstractA variety of [M(L)2(L′)2{κC,C′‐bis(NHC)}]BF4 complexes (M = Rh or Ir; L = CH3CN or wingtip group; L′ = I– or CF3COO–; NHC=N‐heterocyclic carbene) have been tested as pre‐catalysts for the transfer hydrogenation of ketones and imines. The conversions and TOF's obtained are closely related to the nature of the ligand system and metal centre, more strongly coordinating wingtip groups yielding more active and recyclable catalysts. Theoretical calculations at the DFT level support a classic stepwise metal‐hydride pathway against the concerted Meerwein–Ponndorf–Verley (MPV) mechanism. The calculated catalytic cycle involves a series of ligand rearrangements due to the high trans effect of the carbene and hydrido ligands, which are more stable when situated in mutual cis positions. The reaction profiles obtained for the complexes featuring an iodide or a trifluoroacetate in one of the apical positions agree well with the relative activity observed for both catalysts.