A new and efficient method based on the simple metalating reagent Fe(CO)5 has been developed for the straightforward synthesis of well defined cyclometalled PCP iron carbonyl pincer complexes. The reaction proceeds cleanly under mild conditions at 30 °C and UV irradiation. Four hydride pincer complexes are synthesized and fully characterized as well as an intermediate dinuclear species. The new iron complexes are active and selective catalytic precursors for the dehydrogenative borylation of styrene with HBpin.