Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes
Kahlert, J; Böhling, L; Brockhinke, A; Stammler, HG; Neumann, B; Rendina, LM; Low, PJ; Weber, L; Fox, MA
HERO ID
2902151
Reference Type
Journal Article
Year
2015
Language
English
PMID
| HERO ID | 2902151 |
|---|---|
| In Press | No |
| Year | 2015 |
| Title | Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes |
| Authors | Kahlert, J; Böhling, L; Brockhinke, A; Stammler, HG; Neumann, B; Rendina, LM; Low, PJ; Weber, L; Fox, MA |
| Journal | Dalton Transactions (Online) |
| Volume | 44 |
| Issue | 21 |
| Page Numbers | 9766-9781 |
| Abstract | Two C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes, 1-(BMes2)-2-R-1,2-C2B10H10 (, R = H, , 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 and are hydrolysed on prolonged exposure to air to give mesitylene and boronic acids 1-(B(OH)2)-2-R-1,2-C2B10H10 (, R = H, , R = Ph respectively). Addition of fluoride anions to and resulted in boryl-carborane bond cleavage to give dimesitylborinic acid HOBMes2. UV absorption bands at 318-333 nm were observed for and 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 was shown by cyclic voltammetry to form a stable dianion on reduction. NMR spectra for the dianion [](2-) were recorded from solutions generated by reductions of with alkali metals and compared with NMR spectra from reductions of 1,2-diphenyl-ortho-carborane . 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. |
| Doi | 10.1039/c5dt00758e |
| Pmid | 25939355 |
| Wosid | WOS:000355000700008 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |
| Language Text | English |