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

ISSN
1433-7851
Date Issued
2019
Author(s)
Abbenseth, Josh
Delony, Daniel
Neben, Marc C.
de Bruin, Bas
DOI
10.1002/anie.201901470
Abstract
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.
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