TY - JOUR
T1 - Understanding the Origins of Nucleophilic Hydride Reactivity of a Sodium Hydride-Iodide Composite
AU - Hong, Zonghan
AU - Ong, Derek Yiren
AU - Muduli, Subas Kumar
AU - Too, Pei Chui
AU - Chan, Guo Hao
AU - Tnay, Ya Lin
AU - Chiba, Shunsuke
AU - Nishiyama, Yusuke
AU - Hirao, Hajime
AU - Soo, Han Sen
PY - 2016/5/17
Y1 - 2016/5/17
N2 - 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.
AB - 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.
KW - density functional calculations
KW - NMR spectroscopy
KW - sodium hydride-iodide composite
KW - X-ray diffraction
KW - X-ray photoelectron spectroscopy
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U2 - 10.1002/chem.201600340
DO - 10.1002/chem.201600340
M3 - RGC 21 - Publication in refereed journal
SN - 0947-6539
VL - 22
SP - 7108
EP - 7114
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 21
ER -