Synthesis, Structure, and Cyclic Voltammetry of 4,6-Bis(dimesitylboryl)dibenzofuran: Isolation of 4,6-Dilithiobenzofuran and 4,5-Dilithio-9,9-dimethylxanthene as tmeda Adducts
datasetposted on 06.06.2005, 00:00 by Huadong Wang, François P. Gabbaï
The reaction of dibenzofuran and 9,9-dimethylxanthene with sec-BuLi and n-BuLi, respectively, in the presence of N,N,N‘,N‘-tetramethylethylenediamine (tmeda) in hexane followed by storage at −20 °C results in the precipitation of 4,6-dilithiodibenzofuran-1.5(tmeda) (1) and 4,5-dilithio-9,9-dimethylxanthene-1.5(tmeda) (2). Both of these adducts form tetranuclear dimers with the lithium atoms bridging the deprotonated aromatic ligands. The reaction of 1 with dimesitylboronfluoride affords 4,6-bis(dimesitylboryl)dibenzofuran (3), which has been fully characterized. Cyclic voltammetry of compound 3 shows two reduction waves at E1/2 −2.45 and −2.81 V (vs Fc/Fc+), which substantiates significant electronic coupling of the two boron centers. Computational studies show that the p-orbital of the two boron centers participates equally to the LUMO, thus providing grounds for the observed electronic coupling.
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adducts form tetranuclear dimersligandBisSynthesicompoundtetramethylethylenediamineboron centersComputational studies showLUMOVoltammetrydimethylxanthenetmedaFcbidilithiopresenceDilithiobenzofuranIsolationDilithiohexaneAdductdilithiodibenzofurandeprotonatedvsdibenzofuranstoragelithiumvoltammetryCyclicdimesitylboronfluoride