Main-Chain Boron-Containing Oligophenylenes via Ring-Opening Polymerization of 9-H-9-Borafluorene

9-H-9-Borafluorene (H8C12BH; 5) can be generated in situ from 9-Br-9-borafluorene and Et3SiH in benzene or hexane. Monitoring of the reaction by NMR spectroscopy at rt in C6D6 reveals that 5 forms C1-symmetric dimers (5)2 under these conditions. DFT calculations on conceivable isomers of (5)2 and a comparison of calculated and experimentally determined 1H, 13C, and 11B NMR shift values lead to the conclusion that (5)2 is not a classical dimer H8C12B(μ-H)2BC12H8, but contains one B−H−B three-center, two-electron bond together with a boron-bridging phenyl ring. Addition of 1 equiv of pyridine to (5)2 leads to the clean formation of the pyridine adduct H8C12BH(py) (5·py). Likewise, (5)2 can be employed in hydroboration reactions, as evidenced by its transformation with 0.5 equiv of tert-butylacetylene, which gives the hydroboration products tBuC(H)2C(H)(BC12H8)2 (9) and tBuC(H)C(H)BC12H8 in almost quantitative yield. (5)2 is not long-term stable in benzene solution. Addition of pyridine to aged reaction mixtures allowed the isolation of the adduct (py)H2B-C6H4-C6H4-(py)BC12H8 (10·py2) of a ring-opened dimer of 5. Storage of a hexane solution of 9-Br-9-borafluorene and Et3SiH for 1−2 weeks at rt leads to the formation of crystals of a ring-opened pentamer H[-(H)B-(C6H4)2-]4BC12H8 (11) of 5 (preparative yields are obtained after 1−4 months). The polymer main chain of 11 is reinforced by four intrastrand B−H−B three-center, two-electron bonds. Apart from the main product 11, we have also isolated minor amounts of closely related oligomers carrying different chain ends, i.e., H8C12B-(C6H4)2[-(H)B-(C6H4)2-]2BC12H8 (12) and H[-(H)B-(C6H4)2-]5BH2 (13). When the reaction between 9-Br-9-borafluorene and Et3SiH is carried out in refluxing toluene, the cyclic dimer [-(μ-H)B-(C6H4)2-]2 (14) can be obtained in a crystalline yield of 25%. The compounds 9, 10·py2, 11, 12, 13, and 14 have been structurally characterized by X-ray crystallography. The entire reaction pathway leading from 5 to 10, 11, 12, 13, and 14 has been thoroughly elucidated by DFT calculations and we propose a general mechanistic scenario applicable for ring-opening polymerization reactions of 9-borafluorenes.