1,1-Hydroboration and a Borane Adduct of Diphenyldiazomethane: A Potential Prelude to FLP-N2 Chemistry

Connie Tang; Quiming Liang; Andrew R Jupp; Timothy C Johnstone; Rebecca C Neu; Datong Song; Stefan Grimme; Douglas W Stephan

doi:10.1002/anie.201710337

1,1-Hydroboration and a Borane Adduct of Diphenyldiazomethane: A Potential Prelude to FLP-N₂ Chemistry

Angew Chem Int Ed Engl. 2017 Dec 22;56(52):16588-16592. doi: 10.1002/anie.201710337. Epub 2017 Dec 5.

Authors

Connie Tang¹, Quiming Liang¹, Andrew R Jupp¹, Timothy C Johnstone¹, Rebecca C Neu¹, Datong Song¹, Stefan Grimme², Douglas W Stephan¹

Affiliations

¹ Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario, M5S3H6, Canada.
² Mulliken Center for Theoretical Chemistry, Institut fuer Physikalische und Theoretische Chemie, Universitaet Bonn, Beringstrasse 4, 53115, Bonn, Germany.

PMID: 29108092
DOI: 10.1002/anie.201710337

Abstract

Diphenyldiazomethane reacts with HB(C₆ F₅ )₂ and B(C₆ F₅ )₃ , resulting in 1,1-hydroboration and adduct formation, respectively. The hydroboration proceeds via a concerted reaction involving initial formation of the Lewis adduct Ph₂ CN₂ BH(C₆ F₅ )₂ . The highly sensitive adduct Ph₂ CN₂ (B(C₆ F₅ )₃ ) liberates N₂ and generates Ph₂ CB(C₆ F₅ )₃ . DFT computations reveal that formation of Ph₂ CN₂ B(C₆ F₅ )₃ from carbene, N₂ , and borane is thermodynamically favourable, suggesting steric frustration could preclude carbene-borane adduct formation and affect FLP-N₂ capture.

Keywords: adducts; boranes; diphenyldiazomethane; hydroboration; nitrogen.

Publication types

Research Support, Non-U.S. Gov't