Synthesis, bridgehead functionalization, and photoisomerization of 9,10-diboratatriptycene dianions

9,10-Diboratatriptycene salts M2[RB(μ-C6H4)3BR] (R = H, Me; M+ = Li+, K+, [n-Bu4N]+) have been synthesized via [4+2] cycloaddition between doubly reduced 9,10-dihydro-9,10-diboraanthracenes M2[DBA] and benzyne, generated in situ from C6H5F and C6H5Li or LiN(i-Pr)2. [HB(μ-C6H4)3BH]2– reacts with CH2Cl2 to form quantitatively the bridgehead-derivatized [ClB(μ‑C6H4)3BCl]2–, while twofold H– abstraction with B(C6F5)3 in the presence of SMe2 leads cleanly to the diadduct (Me2S)B(μ‑C6H4)3B(SMe2). Photoisomerization of K2[HB(μ-C6H4)3BH] (THF, medium-pressure Hg lamp) provides facile access to diborabenzo[a]fluoranthenes, a little explored form of boron-doped polycyclic aromatic hydrocarbons. According to DFT calculations, the underlying reaction mechanism consists of three main steps: (i) photoinduced di-π-borate rearrangement, (ii) “walk reaction” of a BH unit, and (iii) boryl anion-like C–H activation.