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Ligation of Boratabenzene and 9-Borataphenanthrene to Coinage Metals

https://doi.org/10.1021/acs.inorgchem.1c02800

Wisofsky, Greta K.; Rojales, Katherine; Su, Xiaojun; Bartholome, Tyler A.; Molino, Andrew; Kaur, Aishvaryadeep; Wilson, David J.; Dutton, Jason L.; Martin, Caleb D. (December 2021, Inorganic Chemistry)

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Borataalkene Hydrofunctionalization Reactions

https://doi.org/10.1021/acs.organomet.1c00261

Bartholome, Tyler A.; Martinez, Jesse J.; Kaur, Aishvaryadeep; Wilson, David J.; Dutton, Jason L.; Martin, Caleb D. (June 2021, Organometallics)

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The 9‐Borataphenanthrene Anion

https://doi.org/10.1002/anie.202002125

Bartholome, Tyler A.; Kaur, Aishvaryadeep; Wilson, David J. D.; Dutton, Jason L.; Martin, Caleb D. (May 2020, Angewandte Chemie International Edition)

Abstract The 9‐borataphenanthrene anion is easily accessed by deprotonation of a 9,10‐dihydro‐9‐boraphenanthrene and its diverse reactivity is investigated. Alkylation occurs at the carbon atom adjacent to boron, and room temperature hydroboration occurs across the B=C bond. The π‐manifold of the central BC₅ring coordinates to chromium in an η⁶fashion while only the B=C unit binds η²to gold, indicating versatility of the 9‐borataphenanthrene anion as a ligand. Supporting calculations rationalize the reactivity and aromaticity is corroborated by nucleus‐independent chemical shift (NICS) indices.
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Isolation of Stable Borepin Radicals and Anions

https://doi.org/10.1002/anie.202202516

Hollister, Kimberly K.; Yang, Wenlong; Mondol, Ranajit; Wentz, Kelsie E.; Molino, Andrew; Kaur, Aishvaryadeep; Dickie, Diane A.; Frenking, Gernot; Pan, Sudip; Wilson, David J. D.; et al (April 2022, Angewandte Chemie International Edition)

Abstract Borepin, a 7‐membered boron‐containing heterocycle, has become an emerging molecular platform for the development of new materials and optoelectronics. While electron‐deficient borepins are well‐established, reduced electron‐rich species have remained elusive. Herein we report the first isolable, crystalline borepin radical (2 a,2 b) and anion (3 a,3 b) complexes, which have been synthesized by potassium graphite (KC₈) reduction of cyclic(alkyl)(amino) carbene‐dibenzo[b,d]borepin precursors. Borepin radicals and anions have been characterized by EPR or NMR, elemental analysis, X‐ray crystallography, and cyclic voltammetry. In addition, the bonding features have been investigated computationally using density functional theory.
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