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

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.

SUBMITTER: Abbenseth J 

PROVIDER: S-EPMC6519162 | biostudies-other | 2019 May

REPOSITORIES: biostudies-other

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

Abbenseth Josh J   Delony Daniel D   Neben Marc C MC   Würtele Christian C   de Bruin Bas B   Schneider Sven S  

Angewandte Chemie (International ed. in English) 20190401 19

The isolable complex [Os(PHMes*)H(PNP)] (Mes*=2,4,6-<sup>t</sup> Bu<sub>3</sub> C<sub>6</sub> H<sub>3</sub> ; PNP=N{CHCHP<sup>t</sup> Bu<sub>2</sub> }<sub>2</sub> ) 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 electrophi  ...[more]

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