Among the 2-substituted indenes, 2-trifluoroindene and 2-tert-butylindene are poorly or incompletely described in the open literature. We herein describe an efficient one-pot synthesis of these compounds as a variation of the Perkin reaction which allows us to refute an earlier claim that bis(2-tert-butylindenyl)zirconium(IV) dichloride (2a) will not polymerise ethene. In fact, 2a/MAO polymerises ethene to extremely high molecular weights. Extensive DFT calculations on the polymerisation mechanism revealed an unprecedented suppression of the otherwise predominant chain termination by beta-hydride transfer due to steric congestion of the active site.