The ligand exchange reaction of (THF)Fe[Si(SiMe)] with 2 equivalents of an N-heterocyclic carbene (NHC) led to the formation of a square-planar iron(II) complex with -oriented -Si(SiMe) ligands. Conversely, the introduction of a -coordinate bidentate organosilyl ligand instead of -Si(SiMe) resulted in the formation of a square planar iron(II) complex supported by a -coordinate bidentate organosilyl ligand. A three-coordinate planar iron(II) bis(silyl) complex was also synthesized using a -coordinate bidentate organosilyl ligand and a cyclic (alkyl)(amino)carbene auxiliary ligand. Investigation of the catalytic performance of these complexes in the hydrosilylation of acetophenone revealed that the square-planar iron(II) complex with -oriented -Si(SiMe) ligands exhibits superior reactivity relative to its tetrahedral precursor.
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