A new anthraquinoid ligand for the iron-catalyzed hydrosilylation of carbonyl compounds at room temperature: new insights and kinetics12. Issue 21 (16th May 2018)

• Record Type: Journal Article
• Authors: Raya-Barón, Álvaro; Galdeano-Ruano, Carmen P.; Oña-Burgos, Pascual; Rodríguez-Diéguez, Antonio; Langer, Robert; López-Ruiz, Rosalía; Romero-González, Roberto; Kuzu, Istemi; Fernández, Ignacio
• Is Part Of: Dalton transactions. Volume 47:Issue 21(2018)
• Page Start: 7272
• Page End: 7281
• Publication Date: 2018-05-16
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt01123k
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The synthesis and characterization of a highly active Fe(ii ) catalyst for the hydrosilylation of aldehydes and ketones have been described. 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 Ph2 SiH2 and a fractional order in the case of the catalyst.