From 2,4‐Diphospha‐3‐Thia‐ and ‐3‐Selenapentadienes [(Me₃Si)₂CP]₂E to Heteronorbornane Cage Compounds

Abstract

Cagey characters: Heteronorbornanes (R2CP)2E3 unexpectedly form when selenium or sulfur react with 2,4-diphosphapentadiene derivatives (R2CP)2E (R=Me3Si, E=S, Se; see picture). Calculations on model compounds (R=H3Si, E=S), and synthesized counterparts suggest that the (R2CP)2S3 cage forms after a sequence of CS and PS bond cleavage and formation steps involving SPIII-CR2-S-PV(S)CR2 as an open-chain intermediate.