Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes

Kahlert J, Böhling L, Brockhinke A, Stammler H-G, Neumann B, Rendina LM, Low PJ, Weber L, Fox MA (2015)
Journal of the Chemical Society. Dalton Transactions 44(21): 9766-9781.

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Abstract
Two C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes, 1-(BMes(2))-2-R-1,2-C2B10H10 (1, R = H, 2, R = Ph), were synthesised by lithiation of 1,2-dicarba-closo-dodecaborane and 1-phenyl-1,2-dicarba-closo-dodecaborane, respectively, with n-butyllithium and subsequent reaction with fluorodimesitylborane. These novel compounds were structurally characterised by X-ray crystallography. Compounds 1 and 2 are hydrolysed on prolonged exposure to air to give mesitylene and boronic acids 1-(B(OH)(2))-2-R-1,2-C2B10H10 (3, R = H, 4, R = Ph respectively). Addition of fluoride anions to 1 and 2 resulted in boryl-carborane bond cleavage to give dimesitylborinic acid HOBMes(2). UV absorption bands at 318-333 nm were observed for 1 and 2 corresponding to local pi-pi*-transitions within the dimesitylboryl groups while visible emissions at 541-664 nm with Stokes shifts of 11 920-16 170 cm(-1) were attributed to intra-molecular charge transfer transitions between the mesityl and cluster groups. Compound 2 was shown by cyclic voltammetry to form a stable dianion on reduction. NMR spectra for the dianion [2](2-) were recorded from solutions generated by reductions of 2 with alkali metals and compared with NMR spectra from reductions of 1,2-diphenyl-ortho-carborane 5. On the basis of observed and computed B-11 NMR shifts, these nido-dianions contain bowl-shaped cluster geometries. The carborane is viewed as the electron-acceptor and the mesityl group is the electron-donor in C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes.
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Kahlert J, Böhling L, Brockhinke A, et al. Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes. Journal of the Chemical Society. Dalton Transactions. 2015;44(21):9766-9781.
Kahlert, J., Böhling, L., Brockhinke, A., Stammler, H. - G., Neumann, B., Rendina, L. M., Low, P. J., et al. (2015). Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes. Journal of the Chemical Society. Dalton Transactions, 44(21), 9766-9781.
Kahlert, J., Böhling, L., Brockhinke, A., Stammler, H. - G., Neumann, B., Rendina, L. M., Low, P. J., Weber, L., and Fox, M. A. (2015). Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes. Journal of the Chemical Society. Dalton Transactions 44, 9766-9781.
Kahlert, J., et al., 2015. Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes. Journal of the Chemical Society. Dalton Transactions, 44(21), p 9766-9781.
J. Kahlert, et al., “Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes”, Journal of the Chemical Society. Dalton Transactions, vol. 44, 2015, pp. 9766-9781.
Kahlert, J., Böhling, L., Brockhinke, A., Stammler, H.-G., Neumann, B., Rendina, L.M., Low, P.J., Weber, L., Fox, M.A.: Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes. Journal of the Chemical Society. Dalton Transactions. 44, 9766-9781 (2015).
Kahlert, Jan, Böhling, Lena, Brockhinke, Andreas, Stammler, Hans-Georg, Neumann, Beate, Rendina, Louis M., Low, Paul J., Weber, Lothar, and Fox, Mark A. “Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes”. Journal of the Chemical Society. Dalton Transactions 44.21 (2015): 9766-9781.
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