Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer.
Josh AbbensethDaniel DelonyMarc C NebenChristian WürteleBas de BruinSven SchneiderPublished in: Angewandte Chemie (International ed. in English) (2019)
The isolable complex [Os(PHMes*)H(PNP)] (Mes*=2,4,6-t Bu3 C6 H3 ; PNP=N{CHCHPt Bu2 }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.