Abstract
AbstractCarbon phosphides, CnPm, may have highly promising electronic, optical, and mechanical properties, but they are experimentally almost unexplored materials. Phosphaheteroallenes stabilized by N‐heterocyclic carbenes undergo a one‐electron reduction to yield compounds of the type (L)2C2P2 with diverse structures. The use of imidazolylidenes as ligands L give complexes with a central four‐membered ring C2P2, while more electrophilic cyclic diamidocarbenes (DAC) give a compound with an acyclic π‐conjugated CP−PC unit. Cyclic C2P2 compounds are best described as non‐Kekulé molecules that are stabilized by coordination to the NHC ligands NHC→(C2P2)←NHC. These species can be easily oxidized to give stable radical cations [(NHC)2C2P2]+.. The remarkably stable molecules with an acylic C2P2 core are best described with electron‐sharing bonds (DAC)=C=P−P=C=(DAC).
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