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Synthesis and Characterization of a Sterically Encumbered Homoleptic Tetraalkyliron(III) Ferrate Complex.


ABSTRACT: Homoleptic iron-alkyl complexes have been implicated as key intermediates in iron-catalyzed cross-coupling with simple iron salts. Tetraalkyliron(III) ferrate species have been shown to be accessible with either methyl or benzyl ligands, where the former complex is S = 3/2 and distorted square planar while the latter is a S = 5/2 distorted tetrahedral species. In the current study, a new tetraalkyliron(III) complex is synthesized containing modified methylene substituents that incorporate large trimethylsilyl (TMS) groups to further probe steric and electronic ligand effects in tetraalkyliron(III) complexes by increasing the electron-donating ability of the ligand while retaining steric bulk. Detailed structural and DFT studies provide insight into electronic structure and bonding of the four-coordinate trimethylsilylmethyl iron(III) complex compared to the previously reported analogs containing methyl and benzyl ligands.

SUBMITTER: Sears JD 

PROVIDER: S-EPMC6481957 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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Synthesis and Characterization of a Sterically Encumbered Homoleptic Tetraalkyliron(III) Ferrate Complex.

Sears Jeffrey D JD   Muñoz Salvador B SB   Cuenca Maria Camila Aguilera MCA   Brennessel William W WW   Neidig Michael L ML  

Polyhedron 20181025


Homoleptic iron-alkyl complexes have been implicated as key intermediates in iron-catalyzed cross-coupling with simple iron salts. Tetraalkyliron(III) ferrate species have been shown to be accessible with either methyl or benzyl ligands, where the former complex is <i>S</i> = 3/2 and distorted square planar while the latter is a <i>S</i> = 5/2 distorted tetrahedral species. In the current study, a new tetraalkyliron(III) complex is synthesized containing modified methylene substituents that inco  ...[more]

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