Angewandte Chemie - International Edition
Angewandte Chemie - International Edition
5 years ago

Unsymmetrical, Cyclic Diborenes and Thermal Rearrangement to a Borylborylene

Alfredo Vargas, Ivonne Vollert, Tom Stennett, James Mattock, Holger Braunschweig
Cyclic diboranes(4) based on a chelating monoanionic benzylphosphine linker were prepared by boron-silicon exchange between arylsilanes and B2Br4. Coordination of Lewis bases to the remaining sp2 boron atom yielded unsymmetrical sp3-sp3 diboranes, which were reduced with KC8 to their corresponding trans-diborenes. These compounds were studied by a combination of spectroscopic methods, X-ray diffraction and DFT calculations. PMe3-stabilized diborene 6 was found to undergo thermal rearrangement to gem-diborene 8. DFT calculations on 8 reveal a polar boron-boron bond, and indicate that the compound is best described as a borylborylene.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201800671

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