A1 Journal article (refereed)
The Autoionization of [TiF4] by Cation Complexation with [15]Crown-5 To Give [TiF2([15]crown-5)][Ti4F18] Containing the Tetrahedral [Ti4F18]2- ion (2005)

Decken, A., Jenkins, H. D. B., Knapp, C., Nikiforov, G. B., Passmore, J., & Rautiainen, J. M. (2005). The Autoionization of [TiF4] by Cation Complexation with [15]Crown-5 To Give [TiF2([15]crown-5)][Ti4F18] Containing the Tetrahedral [Ti4F18]2- ion. Angewandte Chemie, 44(48), 7958-7961. https://doi.org/10.1002/anie.200502900

JYU authors or editors

Publication details

All authors or editors: Decken, Andreas; Jenkins, H. Donald B.; Knapp, Carsten; Nikiforov, Grigory B.; Passmore, Jack; Rautiainen, J. Mikko

Journal or series: Angewandte Chemie

ISSN: 1433-7851

eISSN: 1521-3773

Publication year: 2005

Volume: 44

Issue number: 48

Pages range: 7958-7961

Publisher: Wiley-VCH Verlag

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.1002/anie.200502900

Publication open access: Not open

Publication channel open access: 

Abstract

Crown ethers1 promote the autoionization of elements and compounds leading to novel anions, driven by the complexation energy of the corresponding cation. Examples include the autoionization of alkali metals M on reaction with crown ethers to give complexed M+ as well as alkalides and electrides,2 and the autoionization of main-group and transition-metal chlorides to give cationic crown ether complexes and metal chloro anions.3 We report herein the reaction of TiF4 and [15]crown-5 to give [TiF2([15]crown-5)][Ti4F18]⋅0.5 MeCN (1). This is, as far as we are aware, the first autoionization of a metal fluoride on reaction with a crown ether, and suggests that this is a viable preparative route to other related binary fluoro metal anions. [Ti4F18]2− (Figure 1) has overall Td symmetry and is the second example of such a binary [M4X18]2− cage (M=metal, X=halogen), the first being [W4F18]2−.4 Its structure is related to the more-elaborate oxo complexes, for example, [Ti4F12O6]4−,5 and [Ti4O6(OSMe2)12]4+.6 The related [Ti2F9]− ion was claimed to exist in solution,7 and the salts M[Ti2F9] (M=Cs, NF4) have been reported,8 although their X-ray crystal structures were not determined. We predict, on the basis of estimates of the corresponding energetics, that all monocation salts, with the possible exception of those having small cations, favor [Ti2F9]− ions, and salts of dications favor [Ti4F18]2− ions.

Keywords: inorganic compounds; fluorides; titanium; quantum chemistry

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Ministry reporting: Yes

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