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Issue 10, 2015
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Taming the beast: fluoromesityl groups induce a dramatic stability enhancement in boroles

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Abstract

The electron-deficient pentaarylborole 1-(2′,4′,6′-tris(trifluoromethyl)phenyl)-2,3,4,5-tetraphenylborole (1) has been synthesised with the long-term aim of developing borole-based optoelectronic materials. The bulky 2,4,6-tris(trifluoromethyl)phenyl (FMes) group on the boron atom of 1 significantly improves (>600 times) its air stability relative to its mesityl analogue. Moreover, 1 shows good thermal stability without undergoing the dimerisation or isomerisation reactions reported for some other boroles. A triarylborole analogue (2), belonging to a new class of borole with the 3- and 4-positions of the BC4 ring linked by a –(CH2)3– group, has also been synthesised to elucidate the influence of carbon-bonded substituents on the stability of boroles. Both boroles were prepared through the reaction of Li[FMesBF3] and divinyldilithium reagents, a new and general method for borole syntheses. Compound 2 was found to isomerise through a [1,3]-H shift and double-bond rearrangement to an s-trans-butadienylborane species under highly basic (NaOH) conditions. The increased steric crowding at the boron centre through incorporation of the FMes group does not preclude binding of Lewis bases to either 1 or 2, as demonstrated by their fully reversible binding of pyridine. Interestingly, 1 exhibits a blue-shifted absorption spectrum, as compared with its mesityl analogue, a result contrary to previous understanding of the influence of substituent electronics on the absorption spectra of boroles. Most importantly, these boroles exhibit much greater air-stability than previously reported analogues without sacrificing the strong electron-accepting ability that makes boroles so attractive; indeed, 1 and 2 have very low reduction potentials of −1.52 and −1.69 eV vs. Fc/Fc+, respectively.

Graphical abstract: Taming the beast: fluoromesityl groups induce a dramatic stability enhancement in boroles

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Supplementary files

Article information


Submitted
18 Jun 2015
Accepted
10 Jul 2015
First published
13 Jul 2015

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2015,6, 5922-5927
Article type
Edge Article

Taming the beast: fluoromesityl groups induce a dramatic stability enhancement in boroles

Z. Zhang, R. M. Edkins, M. Haehnel, M. Wehner, A. Eichhorn, L. Mailänder, M. Meier, J. Brand, F. Brede, K. Müller-Buschbaum, H. Braunschweig and T. B. Marder, Chem. Sci., 2015, 6, 5922 DOI: 10.1039/C5SC02205C

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