Direct Phenylation of nido -B 10 H 14 .

As a preliminary step toward its condensation into the porous polymer Activated Borane , the thermolysis of nido -B 10 H 14 ( 1 ) 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- nido -B 10 H 13 ( 2 ), isolated in 48% yield (based on consumption of 1 ) and structurally characterized by single-crystal X-ray diffraction analysis, NMR, and mass spectrometry along with other minor products, such as 6-Ph- nido -B 10 H 13 ( 3 ), for which we observe UV-light-driven conversion into 2 via a "vertex-flip" mechanism, and novel diphenylated 5,8-Ph 2 - nido -B 10 H 12 ( 4 ). Together, the phenylated derivatives provide a valuable insight into the assembly of Activated Borane 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 nido -B 10 H 14 , thus opening the door to the straight-forward synthesis of highly luminescent organic-borane hybrid systems.