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Lithium Cyanide Supported by O‐ and N‐Donors
Author(s) -
Budanow Alexandra,
Franz KlausDieter,
Vitze Hannes,
Fink Lothar,
Alig Edith,
Bolte Michael,
Wagner Matthias,
Lerner HansWolfram
Publication year - 2017
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201600220
Subject(s) - chemistry , cyanation , cyanide , diethyl ether , adduct , reagent , lithium (medication) , bromide , thermal stability , medicinal chemistry , solvent , inorganic chemistry , isostructural , nuclear chemistry , organic chemistry , crystal structure , catalysis , medicine , endocrinology
A series of adducts of LiCN, namely [Li(Me 2 CO 3 )CN], [Li(Et 2 CO 3 )CN], and [Li(NMP)CN] (NMP = N ‐methyl‐2‐pyrrolidone) were prepared by treatment of solvent‐free LiCN with the appropriate donor. The starting material for these approaches, donor‐free LiCN, was quantitatively prepared from Me 3 SiCN and Li[Me] in diethyl ether at 0 °C. Alternatively, [Li(NMP)CN] was synthesized by metathesis reaction of LiCl with NaCN in the presence of stoichiometric amounts of NMP. Although [Li(Me 2 CO 3 )CN] and [Li(Et 2 CO 3 )CN] are water‐sensitive compounds and decompose at the exposure to air, [Li(NMP)CN] is stable in air, even at elevated temperatures. The thermal stability of [Li(NMP)CN] was proven by differential thermal analysis (DTA). [Li(NMP)CN] shows thermal stability up to temperatures of about 132 °C. To evaluate the cyanation ability the reactions of 1‐bromooctane and 3‐bromocyclohexene with unsupported LiCN, [Li(NMP)CN], and a mixture of NaCN/LiCl/NMP were investigated. We found that [Li(NMP)CN] as well as LiCl/NaCN/NMP are efficient cyanation reagents comparable to the expensive and air‐sensitive, donor‐free LiCN. A product of the chloride‐cyanide‐bromide exchange could be isolated and structurally characterized by X‐ray diffraction.