Lithium Anionic Dicarbenes or Acetylides: What is in the Name?
The two-fold deprotonation of the C2-arylated 1,3-imidazolium salts (IPr-Ar)X (1-Ar)X (IPr-Ar = ArC{N(Dipp)CH}<sub>2</sub>; Ar = Ph, 4-Me<sub>2</sub>NC<sub>6</sub>H<sub>4</sub> (DMP) or 4-PhC<sub>6</sub>H<sub>4</sub> (Bp); Dipp = 2,6-iPr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) with nBuLi affords the so-called anionic dicarbenes Li(ADC) (2-Ar) (ADC = ArC{N(Dipp)C}<sub>2</sub>). 2-Ar can be used to prepare a variety of main group heterocycles, however their structures in the solid-state remained hitherto unknown. Herein reported single-crystal X-ray diffraction studies reveal an acetylide type [ArC{N(Dipp)}(Dipp)NC≡CLi)]<sub>n</sub> (3-Ar) dimeric (n = 2) or trimeric (n = 3) molecular structure for 2-Ar. Treatment of 3-Ph with Et<sub>3</sub>B cleanly yields the monoanionic carbene Li[(ADC)(BEt<sub>3</sub>)] (4-Ph) featuring a weakly coordinating anion embedded in the same molecular entity. 3-Ar readily undergo reactions with CO<sub>2</sub> and N<sub>2</sub>O to form the ring-closing products Li[(ADC)(CO<sub>2</sub>)<sub>2</sub>] (5-Ar) and Li[(ADC)N<sub>2</sub>O] (6-Ar), respectively.
Authors
- Beate Neumann (ORCID: https://orcid.org/0000-0002-6899-502X)
- Arne Merschel (ORCID: https://orcid.org/0000-0002-8788-7200)
- Henric Steffenfauseweh (ORCID: https://orcid.org/0000-0002-5187-2242)
- Yury V. Vishnevskiy (ORCID: https://orcid.org/0000-0002-7130-6280)
- Hans‐Georg Stammler (ORCID: https://orcid.org/0000-0002-0918-7057)
- Rajendra S. Ghadwal (ORCID: https://orcid.org/0000-0003-2146-5432)
Institutions
- Bielefeld University (DE)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-03-11
- DOI
- https://doi.org/10.1002/anie.202501068
- Citations
- 5
- Primary Topic
- Coordination Chemistry and Organometallics
- Type
- article
- Field-Weighted Citation Impact
- 4.68
Funders
- Deutsche Forschungsgemeinschaft