Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer

The isolable complex [Os(PHMes*)H(PNP)] (Mes*=2,4,6‐(t)Bu(3)C(6)H(3); PNP=N{CHCHP(t)Bu(2)}(2)) exhibits high phosphinyl radical character. This compound offers access to the phosphinidene complex [Os(PMes*)H(PNP)] by P−H proton coupled electron transfer (PCET). The P−H bond dissociation energy (BDE)...

Descripción completa

Detalles Bibliográficos
Autores principales: Abbenseth, Josh, Delony, Daniel, Neben, Marc C., Würtele, Christian, de Bruin, Bas, Schneider, Sven
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2019
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6519162/
https://www.ncbi.nlm.nih.gov/pubmed/30840783
http://dx.doi.org/10.1002/anie.201901470
Descripción
Sumario:The isolable complex [Os(PHMes*)H(PNP)] (Mes*=2,4,6‐(t)Bu(3)C(6)H(3); PNP=N{CHCHP(t)Bu(2)}(2)) exhibits high phosphinyl radical character. This compound offers access to the phosphinidene complex [Os(PMes*)H(PNP)] by P−H proton coupled electron transfer (PCET). The P−H bond dissociation energy (BDE) was determined by isothermal titration calorimetry and supporting DFT computations. The phosphinidene product exhibits electrophilic reactivity as demonstrated by intramolecular C−H activation.

Ejemplares similares