Introduction of Crabtree's iridium‐based hydrogenation catalyst in 1977 marked a paradigm shift both with respect to the role of iridium in homogeneous catalysis as well as catalytic hydrogenation of olefins. In 1998, Pfaltz introduced an improved catalyst, by use of BARF− as anion, and established the first chiral variant of the Crabtree catalyst. This led to numerous practical highly enantioselective syntheses. Elucidation of mechanistic details posed great problems because of instability of the crucial intermediates. A remarkable breakthrough was achieved by Brandt, Andersson et al. in 2003, based on dft calculations. These authors replaced a previously assumed IrI/IrIII catalytic cycle by a novel IrIII/IrV cycle. The proposal was experimentally verified by Pfaltz in 2014 and corroborated by advanced quantum chemical calculations. This essay is an attempt to describe a fascinating interplay of experiments and quantum chemical calculations for an important synthetic method.