Syntheses and Structures of 5-Membered Heterocycles Featuring 1,2-Diphospha-1,3-Butadiene and Its Radical Anion

Mahendra K Sharma; Hanns M Weinert; Bin Li; Christoph Wölper; Justin T Henthorn; George E Cutsail 3rd; Gebhard Haberhauer; Stephan Schulz

doi:10.1002/anie.202309466

Syntheses and Structures of 5-Membered Heterocycles Featuring 1,2-Diphospha-1,3-Butadiene and Its Radical Anion

Angew Chem Int Ed Engl. 2023 Oct 2;62(40):e202309466. doi: 10.1002/anie.202309466. Epub 2023 Aug 29.

Authors

Mahendra K Sharma¹, Hanns M Weinert¹, Bin Li¹, Christoph Wölper¹, Justin T Henthorn², George E Cutsail 3rd², Gebhard Haberhauer³, Stephan Schulz^{1

4}

Affiliations

¹ Institute of Inorganic Chemistry, University of Duisburg-Essen, Universitätsstraße 5-7, 45141, Essen, Germany.
² Max Planck Institute for Chemical Energy Conversion (MPI-CEC), Stiftstrasse 34-36, 45470, Mülheim an der Ruhr, Germany.
³ Institute of Organic Chemistry, University of Duisburg-Essen, Universitätsstraße 5-7, 45141, Essen, Germany.
⁴ Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen, Carl-Benz-Straße 199, 47057, Duisburg, Germany.

PMID: 37582227
DOI: 10.1002/anie.202309466

Abstract

LGa(P₂ OC)cAAC 2 features a 1,2-diphospha-1,3-butadiene unit with a delocalized π-type HOMO and a π*-type LUMO according to DFT calculations. [LGa(P₂ OC)cAAC][K(DB-18-c-6)] 3[K(DB-18-c-6] containing the 1,2-diphospha-1,3-butadiene radical anion 3⋅^- was isolated from the reaction of 2 with KC₈ and dibenzo-18-crown-6. 3 reacted with [Fc][B(C₆ F₅ )₄ ] (Fc=ferrocenium) to 2 and with TEMPO to [L^-H Ga(P₂ OC)cAAC][K(DB-18-c-6)] 4[K(DB-18-c-6] containing the 1,2-diphospha-1,3-butadiene anion 4^- . The solid state structures of 2, 3K(DB-18-c-6], and 4[K(DB-18-c-6] were determined by single crystal X-ray diffraction (sc-XRD).

Keywords: 1,3-Butadienes; Gallium; Main Group Elements; Phosphorus; Radical; π-Conjugation.

Abstract

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