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Chemistry. 2019 Feb 4. doi: 10.1002/chem.201805932. [Epub ahead of print]

A Phosphorus Analogue of p-Quinodimethane with a Planar P4 Ring: A Metal-Free Diphosphorus Source.

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Anorganische Molekülchemie und Katalyse, Anorganische Chemie und Strukturchemie, Centrum für Molekulare Materialien, Fakultät für Chemie, Universität Bielefeld, Universitätsstrasse 25, 33615, Bielefeld, Germany.
Department of Materials Engineering Science, Graduate School of, Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan.
Institute for Molecular Science, 38 Nishigo-Naka, Myodaiji, Okazaki, 444-8585, Japan.


Para-quinodimethane (pQDM) is a fundamental structural component in many π-conjugated organic molecules and materials. The incorporation of phosphorus atom into π-conjugated frameworks offers unique opportunities for controlling the properties of derived species. A phosphorus analogue of p-quinodimethane (pQDM), (IPrC)2 P4 [5, IPr=C{N(Ar)CH2 }2 ; Ar=2,6-iPr2 C6 H3 ] featuring a planar P4 ring, was readily accessible by KC8 -reduction of (IPrC)(PCl2 )2 (2). Base-mediated C-H functionalization of IPrCH2 (1) with PCl3 afforded 2. The formation of 5 was expected to occur through a dimerization of the transient 3H-diphosphirene (IPrC)P2 (4), which was theoretically suggested to have an intermediate diradical character. Compound 5 underwent photo-induced ring-contraction reaction to form the singlet diradicaloid (IPrCP)2 VI and white phosphorus (P4 ). The formation of and VI and P4 suggested the formal diphosphorus (P2 ) elimination from 5. Indeed, photolysis of a mixture of 1,3-cyclohexadiene (CHD) and 5 led to the formation of P2 -entrapped product (CHD)2 P2 (6). The compound 5 represents the first organophosphorus species that functions as a P2 source.


carbenes; diphosphorus; heterocycles; main-group elements; quinodimethane


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