Efficient Hydrosilylation of Acetophenone with a New Anthraquinonic Amide-Based Iron Precatalyst

Álvaro Raya-Barón, Manuel A. Ortuño, Pascual Oña-Burgos, Antonio Rodríguez-Diéguez, Robert Langer, Chris Cramer, Istemi Kuzu, Ignacio Fernández

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14 Scopus citations

Abstract

A new iron complex based on a noninnocent anthraquinonic ligand has been synthesized and fully characterized through multiple techniques, including NMR, X-ray crystallography, mass spectrometry, and cyclic voltammetry. Exposure of ketone to that complex in the presence of (EtO)2MeSiH affords the corresponding silylated alcohol. Loadings as low as 0.25 mol % afford excellent yields at room temperature. Quantum-chemical analysis of the catalytic mechanism supports activation of the precatalyst to form a Fe-hydride intermediate, followed by ketone reduction and σ-bond metathesis.

Original languageEnglish (US)
Pages (from-to)4083-4089
Number of pages7
JournalOrganometallics
Volume35
Issue number24
DOIs
StatePublished - Dec 27 2016

Bibliographical note

Funding Information:
This work was supported by the Junta de Andaluci?a (Spain) under the project number P12-FQM-2668, the U.S. National Science Foundation (CHE-1361595) and by Bruker Espan?ola SA. A.R.-B. and P.O.-B. thank the University of Almeri?a and MEC for a Ph.D. fellowship and a Ramo?n y Cajal contract (RYC-2014-16620), respectively. R.L. is funded by the DFG (LA 2830/3-2). I.K. would like to thank Prof. S. Dehnen for generous support and Prof. B. Neumu?ller for X-ray measurements of 2 and 2b. We acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing resources that contributed to the research results reported within this paper.

Publisher Copyright:
© 2016 American Chemical Society.

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