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

摘要

The isolable complex [Os(PHMes*)H(PNP)] (Mes*=2,4,6-(Bu3C6H3)-Bu-t; PNP=N{(CHCHPBu2)-Bu-t}(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.