The Varied Frustrated Lewis Pair Reactivity of the Germylene Phosphaketene (CH{(CMe)(2,6-i Pr2 C6 H3 N)}2 )GePCO

Yile Wu; Zhao Zhao; Ting Chen; Jingjie Tan; Zheng-Wang Qu; Stefan Grimme; Yufen Zhao; Douglas W Stephan

doi:10.1002/chem.202200666

The Varied Frustrated Lewis Pair Reactivity of the Germylene Phosphaketene (CH{(CMe)(2,6-ⁱ Pr₂ C₆ H₃ N)}₂ )GePCO

Chemistry. 2022 May 2;28(25):e202200666. doi: 10.1002/chem.202200666. Epub 2022 Mar 24.

Authors

Yile Wu^{1

2}, Zhao Zhao¹, Ting Chen¹, Jingjie Tan¹, Zheng-Wang Qu³, Stefan Grimme³, Yufen Zhao^{1

4}, Douglas W Stephan^{1

5}

Affiliations

¹ Institute of Drug Discovery Technology, Ningbo University, Ningbo, 315211, Zhejiang, P. R. China.
² State Key Laboratory of Elemento-Organic Chemistry, Nankai University, 30071, Tianjin, P. R. China.
³ Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4, 53115, Bonn, Germany.
⁴ Department of Chemistry, Xiamen University, Xiamen, 361005, Fujian, P. R. China.
⁵ Department of Chemistry, University of Toronto, 80 St. George St, Toronto, ON, M5S3H6, Canada.

Abstract

The germylene species (CH{(CMe)(2,6-iPr₂ C₆ H₃ N)}₂ )GePCO 1 is shown to react with the Lewis acids (E(C₆ F₅ )₃ E=B, Al). Nonetheless, 1 participates in FLP chemistry with electron deficient alkynes or olefins, acting as an intramolecular FLP. In contrast, in the presence of B(C₆ F₅ )₃ and an electron rich alkyne, 1 behaves as Ge-based nucleophile to effect intermolecular FLP addition to the alkyne. This reactivity demonstrates that the reaction pathway is controlled by the nature of the electrophile and nucleophile generated in solution, as revealed by extensive DFT calculations.

Keywords: DFT calculations; alkyne; frustrated Lewis pairs; germylene; olefin.

Abstract

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