Reduction of silylated 1,3-dichloro-1,3-diphospha-2,4-diazane, [ClP(μ-NHyp)] 2 [Hyp = Si(SiMe 3 ) 3 ], with activated magnesium in dimethoxyethane allowed the isolation and full characterization of the first stable silylated biradicaloid, [P(μ- [a]
The reaction of the singlet biradical [P(μ-NHyp)] 2 (Hyp = hypersilyl, (Me 3 Si) 3 Si) with different isonitriles afforded a series of five-membered N 2 P 2 C 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 NP and one CP 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.
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