Heterocyclopentanediyls vs Heterocyclopentadienes: A Question of Silyl Group Migration.

The reaction of the singlet biradical [P(μ-NHyp)] (Hyp = hypersilyl, (MeSi)Si) with different isonitriles afforded a series of five-membered NPC heterocycles. Depending on the steric bulk of the substituent at the isonitrile, migration of a Hyp group was observed, resulting in two structurally similar but electronically very different isomers. As evidenced by comprehensive spectroscopic and theoretical studies, the heterocyclopentadiene isomer may be regarded as a rather unreactive closed-shell singlet species with one localized N═P and one C═P double bond, whereas the heterocyclopentanediyl isomer represents an open-shell singlet biradical with interesting photochemical properties, such as photoisomerization under irradiation with red light to a [2.1.0]-housane-type species.