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- Title
A Phosphorus Analogue of p‐Quinodimethane with a Planar P<sub>4</sub> Ring: A Metal‐Free Diphosphorus Source.
- Authors
Rottschäfer, Dennis; Neumann, Beate; Stammler, Hans‐Georg; Kishi, Ryohei; Nakano, Masayoshi; Ghadwal, Rajendra S.
- Abstract
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)2P4 [5, IPr=C{N(Ar)CH2}2; Ar=2,6‐iPr2C6H3] 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)2VI 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)2P2 (6). The compound 5 represents the first organophosphorus species that functions as a P2 source. Metal‐free P2 transfer: A phosphorus analogue of p‐quinodimethane [(IPrC)2P4] (5, IPr=1,3‐Bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene),was readily accessible through KC8‐reduction of (IPrC)(PCl2)2 (2). The P4 ring of 5 is perfectly planar and embedded with trans‐apical N‐heterocyclic vinylidene ligands. Compound 5 served as a metal‐free diphosphorus (P2) source, which was captured with 1,3‐cyclohexadiene (CHD), giving P2(CHD)2 (6).
- Subjects
QUINODIMETHANE; PHOSPHORUS; DIMERIZATION; BIRADICALS; ORGANIC cyclic compounds
- Publication
Chemistry - A European Journal, 2019, Vol 25, Issue 13, p3244
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201805932