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Diphosphabenzenes. VII. Reactions of 1,1,3,3‐Tetrakis(dimethylamino)‐1 λ5, 3 λ5‐diphosphete with 5‐Cyano‐1‐pentine and 2‐(Cyanomethyl)‐1‐methylpyrrol 5‐Cyano‐1‐pentine reacts with the equimolar amount of the λ5‐diphosphete 1 to give the λ5‐diphosphinine (λ5‐diphosphabenzene) ( 3 ), while reaction with the double equimolar amount of 1 yields the λ5‐diphosphinine ( 4 ). The acyclic compount 6 is the main product of the reaction between 1 and 2‐(cyanomethyl)‐1‐methylpyrrol, 5 . Melting points of 4 · CH3CN and 6 , and mass, nmr and ir spectra of 3 , 4 , and 6 are reported. The crystal structure of 4 · CH3CN shows an open‐chain ylidic CPCP‐sequence, which is linked to a λ5‐diphosphinine via an ethylene bridge. The X‐ray structure analysis of 6 confirms the existence as an acyclic conjugated double ylid. 相似文献