Cyclic Alkyl(amino) Carbene‐Induced Rearrangement of Ga‐Phosphaketene

Author:

Li Bin12,Wölper Christoph1,Weinert Hanns Micha1ORCID,Siera Hannah3ORCID,Haberhauer Gebhard3ORCID,Schulz Stephan14ORCID

Affiliation:

1. Institute for Inorganic Chemistry University of Duisburg-Essen Universitätsstr. 5–7 45117 Essen Germany

2. Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China) Key Laboratory of Light Energy Conversion Materials of Hunan Province College College of Chemistry and Chemical Engineering Hunan Normal University Changsha 410081 Hunan P. R. China

3. Institute for Organic Chemistry University of Duisburg-Essen Universitätsstr. 5–7 45117 Essen Germany

4. Center for Nanointegration Duisburg-Essen (Cenide) University of Duisburg-Essen Carl-Benz-Straße 199 47057 Duisburg Germany

Abstract

AbstractReactions of LGa(Cl)P(cAAC) (L=HC[C(Me)N(2,6‐iPr2C6H3)]2, MecAAC (MecAAC=1‐(2,6‐di‐iso‐propylphenyl)‐3,3,5,5‐tetramethyl‐pyrrolidin‐2‐ylidene) with NaPCO and NaN3 gave LGa(PCO)P(MecAAC) (1) and LGa(N3)P(MecAAC) (2), respectively. DFT calculations on the nature of compounds 1 and 2 reveal a phosphaalkene rather than a carbene‐phosphinidene structure. The reaction of 1 with MecAAC resulted in a nucleophilic attack of the electron‐rich P atom on the γ‐C backbone of the β‐diketiminate ligand to give compound 3 as the major product and cyclic 1,2‐diphospha‐1,3‐butadiene LGa(P2OC)MecAAC (4) in minor yield.

Funder

Deutsche Forschungsgemeinschaft

Universität Duisburg-Essen

Hunan Normal University

Publisher

Wiley

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