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Title: Understanding the origins of nucleophilic hydride reactivity of a sodium hydride-iodide composite
Authors: Hong, Zonghan
Ong, Derek Yiren
Muduli, Subas Kumar
Too, Pei Chui
Chan, Guo Hao
Tnay, Ya Lin
Chiba, Shunsuke
Nishiyama, Yusuke
Hirao, Hajime
Soo, Han Sen
Keywords: Sodium Hydride–Iodide Composite
Powder X-ray Diffraction
Issue Date: 2016
Source: Hong, Z., Ong, D. Y., Muduli, S. K., Too, P. C., Chan, G. H., Tnay, Y. L., ... Soo, H. S. (2016). Understanding the origins of nucleophilic hydride reactivity of a sodium hydride-iodide composite. Chemistry - A European Journal, 22(21), 7108-7114. doi:10.1002/chem.201600340
Series/Report no.: Chemistry - A European Journal
Abstract: Sodium hydride (NaH) has been commonly used as a Brønsted base in chemical syntheses, while it has rarely been employed to add hydride (H¢) to unsaturated electrophiles. We previously developed a procedure to activate NaH through the addition of a soluble iodide source and found that the new NaH–NaI composite can effect even stereoselective nucleophilic hydride reductions of nitriles, imines, and carbonyl compounds. In this work, we report that mixing NaH with NaI or LiI in tetrahydrofuran (THF) as a solvent provides a new inorganic composite, which consists of NaI interspersed with activated NaH, as revealed by powder X-ray diffraction, and both solid-state NMR and X-ray photoelectron spectroscopies. DFT calculations imply that this remarkably simple inorganic composite, which is comprised of NaH and NaI, gains nucleophilic hydridic character similar to covalent hydrides, resulting in unprecedented and unique hydride donor chemical reactivity.
ISSN: 0947-6539
DOI: 10.1002/chem.201600340
Rights: © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the author created version of a work that has been peer reviewed and accepted for publication by Chemistry - A European Journal, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [].
Fulltext Permission: open
Fulltext Availability: With Fulltext
Appears in Collections:SPMS Journal Articles

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