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

Abstract

Two C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes, 1-(BMes 2)-2-R-1,2-C 2 B 10 H 10 (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-C 2 B 10 H 10 (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 π-π∗-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 intramolecular 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 11 B 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.