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3a,6a‐Diaza‐1,4‐diphosphapentalenes: Synthesis and Complexation with the Organic π‐Acceptor 1,2,4,5‐Tetracyanobenzene

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The reaction of PCl3 with diethyl ketazine and 4-phenylcyclohexanone azine results in the formation of 1,4-dichloro-3a,6a-diaza-1,4-diphosphapentalenes which were reduced by magnesium in THF to give corresponding diazadiphosphapentalenes EtMeDDP  and PhcHexDDP, containing two-coordinate phosphorus atoms. According to the CVA data, the new diazadiphosphapentalenes are strong electron donors showing oxidation peak potentals at 0.34 and 0.10 V, respectively, (vs Ag/AgCl). Interaction of 1,2,4,5-tetracyanobenzene (TCNB) with obtaining diazadiphosphapentalenes in any stoichiometry produces sandwich complexes of the composition DDP-TCNB-DDP. Black-purple crystals of π-complexes contain infinite molecular chains with short P∙∙∙P contacts between DDP molecules and short (Csp2−H···N) contacts between TCNB molecules. Calculations showed that each TCNB molecule is an acceptor of ~0.3e from two DDP molecules. Estimation of the HOMO−LUMO gap from the onset of optical absorption give values of 1.25 eV and 1.31 eV for [(EtMeDDP)2(TCNB)] and [(PhcHexDDP)2(TCNB)] respectively.

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