Direct Phenylation of nido -B 10 H 14 .

As a preliminary step toward its condensation into the porous polymer , the thermolysis of -BH () in benzene at 200 °C results in the generation of a number of phenylated borane molecular species. The principal product is the new monophenylated compound 5-Ph--BH (), isolated in 48% yield (based on consumption of ) and structurally characterized by single-crystal X-ray diffraction analysis, NMR, and mass spectrometry along with other minor products, such as 6-Ph--BH (), for which we observe UV-light-driven conversion into via a "vertex-flip" mechanism, and novel diphenylated 5,8-Ph--BH (). Together, the phenylated derivatives provide a valuable insight into the assembly of and ultimately inform on its structure. The new compounds also display strong blue fluorescence in both solid-state and in solution and are the first examples of the direct phenylation of -BH, thus opening the door to the straight-forward synthesis of highly luminescent organic-borane hybrid systems.