Syntheses, Structures, Electrochemistry and Optical Properties of Alkyne‐Functionalized 1,3,2‐Diazaboroles and 1,3,2‐Diazaborolidenes
The reaction of 2‐bromo‐1,3‐ditert‐butyl‐2,3‐dihydro‐1H‐1,3,2‐diazaborole (3) with lithiated tert‐butyl‐acetylene and lithiated phenylacetylene affords the 2‐alkynyl‐functionalized 1,3,2‐diazaboroles 4 and 5 as a thermolabile colorless oil (4) or a solid (5). Similarly 2‐bromo‐1,3‐diethyl‐2,3‐dihydro‐1H‐1,3,2‐benzodiazaborole (6) was converted into the crystalline 2‐alkynyl‐benzo‐1,3,2‐diazaboroles 7 and 8 by treatment with LiC≡C–tBu or LiC≡CPh, respectively. 2‐Ethynyl‐1,3‐ditert‐butyl‐2,3‐dihydro‐1H‐1,3,2‐diazaborole (2) was metalated with tert‐butyl‐lithium and subsequently coupled with 2‐bromo‐1,3,‐ditert‐butyl‐2,3‐dihydro‐1H‐1,3,2‐diazaborole (3) to afford bis(1,3‐ditert‐butyl‐2,3‐dihydro‐1H‐1,3,2‐diazaborol‐2‐yl)acetylene (9) as thermolabile colorless crystals. Analogously coupling of the lithiated species with 6 or with 2‐bromo‐1,3‐ditert‐butyl‐1,3,2‐diazaborolidine (11) gave the unsymmetrically substituted acetylenes 10 or 12, respectively, as colorless solids. Compounds 4, 5, 7–10 and 12 are characterized by elemental analyses and spectroscopy (IR, 1H‐, 11B{1H}, 13C{1H}‐NMR, MS). The molecular structures of 5, 8 and 9 were elucidated by X‐ray diffraction analyses.