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Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer
Author(s) -
Abbenseth Josh,
Delony Daniel,
Neben Marc C.,
Würtele Christian,
de Bruin Bas,
Schneider Sven
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201901470
Subject(s) - phosphinidene , chemistry , intramolecular force , electrophile , reactivity (psychology) , electron transfer , medicinal chemistry , photochemistry , proton , isothermal titration calorimetry , bond dissociation energy , stereochemistry , dissociation (chemistry) , crystallography , organic chemistry , catalysis , medicine , physics , alternative medicine , pathology , quantum mechanics
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.