Reactions of Diethylazo-Dicarboxylate with Frustrated Lewis Pairs

Dipendu Mandal; Ting Chen; Zheng-Wang Qu; Stefan Grimme; Douglas W Stephan

doi:10.1002/chem.202201701

Reactions of Diethylazo-Dicarboxylate with Frustrated Lewis Pairs

Chemistry. 2022 Sep 22;28(53):e202201701. doi: 10.1002/chem.202201701. Epub 2022 Jul 27.

Authors

Dipendu Mandal¹, Ting Chen¹, Zheng-Wang Qu², Stefan Grimme², Douglas W Stephan^{1

3}

Affiliations

¹ Institute of Drug Discovery Technology, Ningbo University, 315211, Zhejiang, P. R. China.
² Mulliken Center for Theoretical Chemistry, Clausius Institut für Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Beringstrasse 4, 53115, Bonn, Germany.
³ Department of Chemistry, University of Toronto, 80 St. George St, M5S3H6, Toronto, ON, Canada.

Abstract

Reactions of PAr₃ /B(C₆ F₅ )₃ (Ar=o-Tol, Mes, Ph) FLPs with diethyl azodicarboxylate (DEAD) afford the corresponding FLP addition products 1-3 in which P-N and B-O linkages are formed. In contrast, the reaction of BPh₃ , PPh₃ and DEAD gave product 4 where P-N and N-B linkages were confirmed. In all cases, other binding modes were computed to be both higher in energy and readily distinguishable by ³¹ P and ¹¹ B NMR parameters. These data illustrate the influence of steric demands and electronic structures on the nature of the products of FLP reactions with DEAD.

Keywords: borane; density functional calculations; diethyl azodicarboxylate; frustrated Lewis pairs; phosphines.

Abstract

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