Sterically demanding organosilyl ligands support the formation of coordinatively unsaturated complexes. In this study, we found that using the ligand -Si(SiMe)(SiMeBu) affords exclusively planar three-coordinate iron bis(silyl) complexes that show good catalytic performance in the hydrosilylation of acetophenone.
View Article and Find Full Text PDFThe 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.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2023
So far, Zn(II)-based d complexes have been known to be colorless unless they are accompanied by chromophoric groups, and therefore both fundamental and advanced photophysical performance of Zn centers of complexes, especially in visible-light regions has been unexplored. Here, we first demonstrate a dinuclear Zn(II) complex that shows visible light absorption using an orbital distributed over closely contacted two Zn centers experimentally determined by X-ray crystallography. A contrastive study demonstrated that intermetallic orbital interaction in dinuclear Zn(II) complex is responsible for capturing visible light to exhibit orangish yellow color, whereas an analogous one without such an interaction is colorless.
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