The combined use of aminocarbene and divinyltetramethyldisiloxane (dvtms) as supporting ligands enables the access of unprecedented low-coordinate iron(0) alkene compounds [L(n)Fe(η(2):η(2)-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 {L(n)Fe(0)} 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.
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