Synthetic precursors for TCNQF(4)(2-) compounds: synthesis, characterization, and electrochemical studies of (Pr4N)(2)TCNQF(4) and Li(2)TCNQF(4)

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Abstract

Careful control of the reaction stoichiometry and conditions enables the synthesis of both LiTCNQF(4) and Li(2)TCNQF(4) to be achieved. Reaction of LiI with TCNQF(4), in a 4:1 molar ratio, in boiling acetonitrile yields Li2TCNQF4. However, deviation from this ratio or the reaction temperature gives either LiTCNQF(4) or a mixture of Li(2)TCNQF(4) and LiTCNQF(4). This is the first report of the large-scale chemical synthesis of Li(2)TCNQF(4). Attempts to prepare a single crystal of Li(2)TCNQF(4) have been unsuccessful, although air stable (Pr4N)(2)TCNQF(4) was obtained by mixing Pr4NBr with Li(2)TCNQF(4) in aqueous solution. Pr(4)NTCNQF(4) was also obtained by reaction of LiTCNQF(4) with Pr4NBr in water. Li(2)TCNQF(4), (Pr4N)(2)TCNQF(4), and Pr(4)NTCNQF(4) have been characterized by UV-vis, FT-IR, Raman, and NMR spectroscopy, high resolution electrospray ionization mass spectrometry, and electrochemistry. The structures of single crystals of (Pr4N)(2)TCNQF(4) and Pr(4)NTCNQF(4) have been determined by X-ray crystallography. These TCNQF(4)(2-) salts will provide useful precursors for the synthesis of derivatives of the dianions.
Original languageEnglish
Pages (from-to)10568 - 10574
Number of pages7
JournalJournal of Organic Chemistry
Volume77
Issue number23
DOIs
Publication statusPublished - 2012

Cite this

@article{611bca21a3a1458a990eb7de0927d2fb,
title = "Synthetic precursors for TCNQF(4)(2-) compounds: synthesis, characterization, and electrochemical studies of (Pr4N)(2)TCNQF(4) and Li(2)TCNQF(4)",
abstract = "Careful control of the reaction stoichiometry and conditions enables the synthesis of both LiTCNQF(4) and Li(2)TCNQF(4) to be achieved. Reaction of LiI with TCNQF(4), in a 4:1 molar ratio, in boiling acetonitrile yields Li2TCNQF4. However, deviation from this ratio or the reaction temperature gives either LiTCNQF(4) or a mixture of Li(2)TCNQF(4) and LiTCNQF(4). This is the first report of the large-scale chemical synthesis of Li(2)TCNQF(4). Attempts to prepare a single crystal of Li(2)TCNQF(4) have been unsuccessful, although air stable (Pr4N)(2)TCNQF(4) was obtained by mixing Pr4NBr with Li(2)TCNQF(4) in aqueous solution. Pr(4)NTCNQF(4) was also obtained by reaction of LiTCNQF(4) with Pr4NBr in water. Li(2)TCNQF(4), (Pr4N)(2)TCNQF(4), and Pr(4)NTCNQF(4) have been characterized by UV-vis, FT-IR, Raman, and NMR spectroscopy, high resolution electrospray ionization mass spectrometry, and electrochemistry. The structures of single crystals of (Pr4N)(2)TCNQF(4) and Pr(4)NTCNQF(4) have been determined by X-ray crystallography. These TCNQF(4)(2-) salts will provide useful precursors for the synthesis of derivatives of the dianions.",
author = "Jinzhen Lu and Le, {Thanh Hai} and Traore, {Daouda A K} and Wilce, {Matthew Charles James} and Bond, {Alan Maxwell} and Martin, {Lisandra Lorraine}",
year = "2012",
doi = "10.1021/jo301403v",
language = "English",
volume = "77",
pages = "10568 -- 10574",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "23",

}

TY - JOUR

T1 - Synthetic precursors for TCNQF(4)(2-) compounds: synthesis, characterization, and electrochemical studies of (Pr4N)(2)TCNQF(4) and Li(2)TCNQF(4)

AU - Lu, Jinzhen

AU - Le, Thanh Hai

AU - Traore, Daouda A K

AU - Wilce, Matthew Charles James

AU - Bond, Alan Maxwell

AU - Martin, Lisandra Lorraine

PY - 2012

Y1 - 2012

N2 - Careful control of the reaction stoichiometry and conditions enables the synthesis of both LiTCNQF(4) and Li(2)TCNQF(4) to be achieved. Reaction of LiI with TCNQF(4), in a 4:1 molar ratio, in boiling acetonitrile yields Li2TCNQF4. However, deviation from this ratio or the reaction temperature gives either LiTCNQF(4) or a mixture of Li(2)TCNQF(4) and LiTCNQF(4). This is the first report of the large-scale chemical synthesis of Li(2)TCNQF(4). Attempts to prepare a single crystal of Li(2)TCNQF(4) have been unsuccessful, although air stable (Pr4N)(2)TCNQF(4) was obtained by mixing Pr4NBr with Li(2)TCNQF(4) in aqueous solution. Pr(4)NTCNQF(4) was also obtained by reaction of LiTCNQF(4) with Pr4NBr in water. Li(2)TCNQF(4), (Pr4N)(2)TCNQF(4), and Pr(4)NTCNQF(4) have been characterized by UV-vis, FT-IR, Raman, and NMR spectroscopy, high resolution electrospray ionization mass spectrometry, and electrochemistry. The structures of single crystals of (Pr4N)(2)TCNQF(4) and Pr(4)NTCNQF(4) have been determined by X-ray crystallography. These TCNQF(4)(2-) salts will provide useful precursors for the synthesis of derivatives of the dianions.

AB - Careful control of the reaction stoichiometry and conditions enables the synthesis of both LiTCNQF(4) and Li(2)TCNQF(4) to be achieved. Reaction of LiI with TCNQF(4), in a 4:1 molar ratio, in boiling acetonitrile yields Li2TCNQF4. However, deviation from this ratio or the reaction temperature gives either LiTCNQF(4) or a mixture of Li(2)TCNQF(4) and LiTCNQF(4). This is the first report of the large-scale chemical synthesis of Li(2)TCNQF(4). Attempts to prepare a single crystal of Li(2)TCNQF(4) have been unsuccessful, although air stable (Pr4N)(2)TCNQF(4) was obtained by mixing Pr4NBr with Li(2)TCNQF(4) in aqueous solution. Pr(4)NTCNQF(4) was also obtained by reaction of LiTCNQF(4) with Pr4NBr in water. Li(2)TCNQF(4), (Pr4N)(2)TCNQF(4), and Pr(4)NTCNQF(4) have been characterized by UV-vis, FT-IR, Raman, and NMR spectroscopy, high resolution electrospray ionization mass spectrometry, and electrochemistry. The structures of single crystals of (Pr4N)(2)TCNQF(4) and Pr(4)NTCNQF(4) have been determined by X-ray crystallography. These TCNQF(4)(2-) salts will provide useful precursors for the synthesis of derivatives of the dianions.

U2 - 10.1021/jo301403v

DO - 10.1021/jo301403v

M3 - Article

VL - 77

SP - 10568

EP - 10574

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 23

ER -