(Aminocarbene)(Divinyltetramethyldisiloxane)Iron(0) Compounds: A Class of Low‐Coordinate Iron(0) Reagents

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 FeCl 2 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 Ph 2 SiH 2 , S 8 , Se, and DippN 3 , 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.