The combined use of aminocarbene and divinyltetramethyldisiloxane (dvtms) as supporting ligands enables the access of unprecedented low‐coordinate iron(0) alkene compounds [LnFe(η2:η2‐dvtms)] (L=N‐heterocyclic carbene (NHC) or cyclic (alkyl)(amino)carbene (CAAC), n=1 or 2) from the reactions of FeCl2 with alkali‐metal reducing agents, free aminocarbene ligands, and dvtms. The iron(0) species deliver their {LnFe0} fragments to perform redox reactions with Ph2SiH2, S8, Se, and DippN3, furnishing novel aminocarbene‐supported iron(IV) silylene, all‐ferrous iron–sulfur/selenium cubanes, and bis(imido)iron(IV) compounds. These conversions demonstrate the potential synthetic utility of the carbene‐supported iron(0) complexes as a valuable class of low‐coordinate iron(0) reagents.