Direct Phenylation of nido-B10H14

As a preliminary step toward its condensation into the porous polymer Activated Borane, the thermolysis of nido-B10H14 (1) in benzene at 200 ? results in the generation of a number of phenylated borane molecular species. The principal product is the new mono-phenylated compound 5-Ph-nido-B10H14 (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-B10H13 (3), for which we observe UV-light-driven conversion into 2 via a vertex-flip mechanism, and novel diphenylated 5,8-Ph2-nido-B10H12 (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-B10H14 , thus opening the door to the straight-forward synthesis of highly luminescent organic-borane hybrid systems.

Automated summary

The thermolysis of nido-B10H14 in benzene generates several phenylated borane molecular species, with 5-Ph-nido-B10H14 being the main product. These phenylated compounds provide valuable insights into the assembly and structure of Activated Borane, and exhibit strong blue fluorescence. They also enable the straightforward synthesis of highly luminescent organic-borane hybrid systems.