6533b7d1fe1ef96bd125d74a
RESEARCH PRODUCT
Phosphorus-Chalcogen Ring Expansion and Metal Coordination
Heikki M. TuononenPaul J. RagognaJuuso ValjusCameron M. E. GrahamPaul D. BoyleTaylor E. Pritchardsubject
metal coordination010405 organic chemistryChemistryInorganic chemistryCoinage metals010402 general chemistryRing (chemistry)01 natural sciences0104 chemical sciencesInorganic ChemistryMetalCrystallographyChalcogenring expansionOxidation statePhosphinidenevisual_artvisual_art.visual_art_mediumReactivity (chemistry)Lewis acids and basesPhysical and Theoretical Chemistryphosphorus-chalcogenta116description
The reactivity of 4-membered (RPCh)2 rings (Ch = S, Se) that contain phosphorus in the +3 oxidation state is reported. These compounds undergo ring expansion to (RPCh)3 with the addition of a Lewis base. The 6-membered rings were found to be more stable than the 4-membered precursors, and the mechanism of their formation was investigated experimentally and by density functional theory calculations. The computational work identified two plausible mechanisms involving a phosphinidene chalcogenide intermediate, either as a free species or stabilized by a suitable base. Both the 4- and 6-membered rings were found to react with coinage metals, giving the same products: (RPCh)3 rings bound to the metal center from the phosphorus atom in tripodal fashion. peerReviewed
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2017-01-01 |