Four- and three-coordinate planar iron(II) complexes supported by bulky organosilyl ligands

Reon Ishii; Minesato Nakagawa; Yoshimasa Wada; Yusuke Sunada

doi:10.1039/d3dt02219f

Four- and three-coordinate planar iron(II) complexes supported by bulky organosilyl ligands

Dalton Trans. 2023 Oct 24;52(41):15124-15130. doi: 10.1039/d3dt02219f.

Authors

Reon Ishii¹, Minesato Nakagawa¹, Yoshimasa Wada^{1

2}, Yusuke Sunada^{1

2

3}

Affiliations

¹ Department of Applied Chemistry, School of Engineering, The University of Tokyo, 4-6-1, Komaba, Meguro-ku, Tokyo 153-8505, Japan. sunada@iis.u-tokyo.ac.jp.
² Institute of Industrial Science, The University of Tokyo, 4-6-1, Komaba, Meguro-ku, Tokyo 153-8505, Japan.
³ JST PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan.

PMID: 37814966
DOI: 10.1039/d3dt02219f

Abstract

The ligand exchange reaction of (THF)₂Fe[Si(SiMe₃)₃]₂ with 2 equivalents of an N-heterocyclic carbene (NHC) led to the formation of a square-planar iron(II) complex with trans-oriented -Si(SiMe₃)₃ ligands. Conversely, the introduction of a cis-coordinate bidentate organosilyl ligand instead of -Si(SiMe₃)₃ resulted in the formation of a square planar iron(II) complex supported by a cis-coordinate bidentate organosilyl ligand. A three-coordinate planar iron(II) bis(silyl) complex was also synthesized using a cis-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 trans-oriented -Si(SiMe₃)₃ ligands exhibits superior reactivity relative to its tetrahedral precursor.