Crystallographic insights into the behavior of highly acidic metal cations in ionic liquids from ractions of titanium tetrachloride with [1-butyl-3-methylimidazolium][X] ionic liquids (X = chloride, bromide, tetrafluoroborate)

Manish Kumar Mishra; Steven P. Kelley; Meghna Dilip; Thomas P. Vaid; David B. Cordes; Scott T. Griffin; Robin D. Rogers

doi:10.1021/acs.inorgchem.8b00524

Crystallographic insights into the behavior of highly acidic metal cations in ionic liquids from ractions of titanium tetrachloride with [1-butyl-3-methylimidazolium][X] ionic liquids (X = chloride, bromide, tetrafluoroborate)

Manish Kumar Mishra, Steven P. Kelley, Meghna Dilip, Thomas P. Vaid, David B. Cordes, Scott T. Griffin, Robin D. Rogers^*

^*Corresponding author for this work

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Abstract

Highly charged metal ions are difficult to investigate in weakly coordinating ionic liquids (ILs) because of the insolubility of their solid forms, but the molecular liquid TiCl₄ offers a way to react tetravalent metal ions in an IL. Reactions of TiCl₄ with 1-butyl-3-methylimidazolium ([C₄mim]⁺)-based ILs containing chloride or bromide lead to mixtures of highly metastable amorphous solids and small amounts of crystalline chlorotitanate salts including [C₄mim]₂[TiCl₆] and two polymorphs of [C₄mim]₂[Ti₂Cl₁₀] in a manner not well correlated with stoichiometry or anion identity. The reaction of TiCl₄ with [C₄mim][BF₄] yields crystals of the mixed fluoro-chloro complex [C₄mim]₂[Ti₄F₆Cl₁₂], indicating spontaneous reaction of the IL ions to generate HF in situ. These unusual behaviors are explained in terms of the exceptionally high acidity of Ti⁴⁺ and the unusual behavior of TiCl₄ among metal halides as a nonpolar molecular compound.

Original language	English
Pages (from-to)	1764-1773
Journal	Inorganic Chemistry
Volume	58
Issue number	3
Early online date	14 Jan 2019
DOIs	https://doi.org/10.1021/acs.inorgchem.8b00524
Publication status	Published - 4 Feb 2019

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Copyright © 2019 American Chemical Society. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1021/acs.inorgchem.8b00524
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Crystallographic insights into the behavior of highly acidic metal cations in ionic liquids from ractions of titanium tetrachloride with [1-butyl-3-methylimidazolium][X] ionic liquids (X = chloride, bromide, tetrafluoroborate) (crystallography data)
Mishra, M. K. (Creator), Kelley, S. P. (Creator), Dilip, M. (Creator), Vaid, T. P. (Creator), Cordes, D. B. (Creator), Griffin, S. T. (Creator) & Rogers, R. D. (Creator), Cambridge Crystallographic Data Centre, 17 Feb 2018
https://doi.org/10.5517/ccdc.csd.cc1z7jlb and 2 more links, https://doi.org/10.5517/ccdc.csd.cc1z7jmc, https://doi.org/10.5517/ccdc.csd.cc1z7jnd (show fewer)
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Mishra, M. K., Kelley, S. P., Dilip, M., Vaid, T. P., Cordes, D. B., Griffin, S. T., & Rogers, R. D. (2019). Crystallographic insights into the behavior of highly acidic metal cations in ionic liquids from ractions of titanium tetrachloride with [1-butyl-3-methylimidazolium][X] ionic liquids (X = chloride, bromide, tetrafluoroborate). Inorganic Chemistry, 58(3), 1764-1773. https://doi.org/10.1021/acs.inorgchem.8b00524

@article{a7b061748b5a47148ba973178b12e520,

title = "Crystallographic insights into the behavior of highly acidic metal cations in ionic liquids from ractions of titanium tetrachloride with [1-butyl-3-methylimidazolium][X] ionic liquids (X = chloride, bromide, tetrafluoroborate)",

abstract = "Highly charged metal ions are difficult to investigate in weakly coordinating ionic liquids (ILs) because of the insolubility of their solid forms, but the molecular liquid TiCl4 offers a way to react tetravalent metal ions in an IL. Reactions of TiCl4 with 1-butyl-3-methylimidazolium ([C4mim]+)-based ILs containing chloride or bromide lead to mixtures of highly metastable amorphous solids and small amounts of crystalline chlorotitanate salts including [C4mim]2[TiCl6] and two polymorphs of [C4mim]2[Ti2Cl10] in a manner not well correlated with stoichiometry or anion identity. The reaction of TiCl4 with [C4mim][BF4] yields crystals of the mixed fluoro-chloro complex [C4mim]2[Ti4F6Cl12], indicating spontaneous reaction of the IL ions to generate HF in situ. These unusual behaviors are explained in terms of the exceptionally high acidity of Ti4+ and the unusual behavior of TiCl4 among metal halides as a nonpolar molecular compound.",

author = "Mishra, {Manish Kumar} and Kelley, {Steven P.} and Meghna Dilip and Vaid, {Thomas P.} and Cordes, {David B.} and Griffin, {Scott T.} and Rogers, {Robin D.}",

year = "2019",

month = feb,

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doi = "10.1021/acs.inorgchem.8b00524",

language = "English",

volume = "58",

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Mishra, MK, Kelley, SP, Dilip, M, Vaid, TP, Cordes, DB, Griffin, ST & Rogers, RD 2019, 'Crystallographic insights into the behavior of highly acidic metal cations in ionic liquids from ractions of titanium tetrachloride with [1-butyl-3-methylimidazolium][X] ionic liquids (X = chloride, bromide, tetrafluoroborate)', Inorganic Chemistry, vol. 58, no. 3, pp. 1764-1773. https://doi.org/10.1021/acs.inorgchem.8b00524

Crystallographic insights into the behavior of highly acidic metal cations in ionic liquids from ractions of titanium tetrachloride with [1-butyl-3-methylimidazolium][X] ionic liquids (X = chloride, bromide, tetrafluoroborate). / Mishra, Manish Kumar; Kelley, Steven P.; Dilip, Meghna et al.
In: Inorganic Chemistry, Vol. 58, No. 3, 04.02.2019, p. 1764-1773.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Crystallographic insights into the behavior of highly acidic metal cations in ionic liquids from ractions of titanium tetrachloride with [1-butyl-3-methylimidazolium][X] ionic liquids (X = chloride, bromide, tetrafluoroborate)

AU - Mishra, Manish Kumar

AU - Kelley, Steven P.

AU - Dilip, Meghna

AU - Vaid, Thomas P.

AU - Cordes, David B.

AU - Griffin, Scott T.

AU - Rogers, Robin D.

PY - 2019/2/4

Y1 - 2019/2/4

N2 - Highly charged metal ions are difficult to investigate in weakly coordinating ionic liquids (ILs) because of the insolubility of their solid forms, but the molecular liquid TiCl4 offers a way to react tetravalent metal ions in an IL. Reactions of TiCl4 with 1-butyl-3-methylimidazolium ([C4mim]+)-based ILs containing chloride or bromide lead to mixtures of highly metastable amorphous solids and small amounts of crystalline chlorotitanate salts including [C4mim]2[TiCl6] and two polymorphs of [C4mim]2[Ti2Cl10] in a manner not well correlated with stoichiometry or anion identity. The reaction of TiCl4 with [C4mim][BF4] yields crystals of the mixed fluoro-chloro complex [C4mim]2[Ti4F6Cl12], indicating spontaneous reaction of the IL ions to generate HF in situ. These unusual behaviors are explained in terms of the exceptionally high acidity of Ti4+ and the unusual behavior of TiCl4 among metal halides as a nonpolar molecular compound.

AB - Highly charged metal ions are difficult to investigate in weakly coordinating ionic liquids (ILs) because of the insolubility of their solid forms, but the molecular liquid TiCl4 offers a way to react tetravalent metal ions in an IL. Reactions of TiCl4 with 1-butyl-3-methylimidazolium ([C4mim]+)-based ILs containing chloride or bromide lead to mixtures of highly metastable amorphous solids and small amounts of crystalline chlorotitanate salts including [C4mim]2[TiCl6] and two polymorphs of [C4mim]2[Ti2Cl10] in a manner not well correlated with stoichiometry or anion identity. The reaction of TiCl4 with [C4mim][BF4] yields crystals of the mixed fluoro-chloro complex [C4mim]2[Ti4F6Cl12], indicating spontaneous reaction of the IL ions to generate HF in situ. These unusual behaviors are explained in terms of the exceptionally high acidity of Ti4+ and the unusual behavior of TiCl4 among metal halides as a nonpolar molecular compound.

U2 - 10.1021/acs.inorgchem.8b00524

DO - 10.1021/acs.inorgchem.8b00524

M3 - Article

AN - SCOPUS:85060205957

SN - 0020-1669

VL - 58

SP - 1764

EP - 1773

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 3

ER -

Mishra MK, Kelley SP, Dilip M, Vaid TP, Cordes DB, Griffin ST et al. Crystallographic insights into the behavior of highly acidic metal cations in ionic liquids from ractions of titanium tetrachloride with [1-butyl-3-methylimidazolium][X] ionic liquids (X = chloride, bromide, tetrafluoroborate). Inorganic Chemistry. 2019 Feb 4;58(3):1764-1773. Epub 2019 Jan 14. doi: 10.1021/acs.inorgchem.8b00524

Crystallographic insights into the behavior of highly acidic metal cations in ionic liquids from ractions of titanium tetrachloride with [1-butyl-3-methylimidazolium][X] ionic liquids (X = chloride, bromide, tetrafluoroborate)

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Crystallographic insights into the behavior of highly acidic metal cations in ionic liquids from ractions of titanium tetrachloride with [1-butyl-3-methylimidazolium][X] ionic liquids (X = chloride, bromide, tetrafluoroborate) (crystallography data)

Cite this