A new anthraquinoid ligand for the iron-catalyzed hydrosilylation of carbonyl compounds at room temperature: new insights and kinetics

Dalton Transactions : an International Journal of Inorganic Chemistry
Álvaro Raya-BarónIgnacio Fernández

Abstract

The reaction of 1-((2-(pyridin-2-yl)ethyl)amino)anthraquinone with either Fe(HMDS)2 or Li(HMDS)/FeCl2 allowed the preparation of a new anthraquinoid-based iron(ii) complex active in the hydrosilylations of carbonyls. The new complex Fe(2)2 was characterized by single-crystal X-ray diffraction, infrared spectroscopy, NMR, and high resolution mass spectrometry (electrospray ionization). Superconducting quantum interference device (SQUID) magnetometry established no spin crossover behavior with an S = 2 state at room temperature. This complex was determined to be an effective catalyst for the hydrosilylation of aldehydes and ketones, exhibiting turnover frequencies of up to 63 min-1 with a broad functional group tolerance by just using 0.25 mol% of the catalyst at room temperature, and even under solvent-free conditions. The aldehyde hydrosilylation makes it one of the most efficient first-row transition metal catalysts for this transformation. Kinetic studies have proven first-order dependences with respect to acetophenone and Ph2SiH2 and a fractional order in the case of the catalyst.

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Citations

Aug 29, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Ana Belén Ruiz-MuelleIgnacio Fernández
Jun 4, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Cristina RuizIgnacio Fernández
Jul 3, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Guoliang ChangDieter Fenske

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Methods Mentioned

BETA
NMR
X-ray
column chromatography

Software Mentioned

SHELX
SIR97
97
APEX2
WINGX
Elementar

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