Photocatalytic Arylation of P 4 and PH 3 : Reaction Development Through Mechanistic Insight

Detailed 31 P{ 1 H} NMR spectroscopic investigations provide deeper insight into the complex, multi‐step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P 4 ). Specifically, these studies have identified a number of previously unrecognized side products, wh...

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Bibliographic Details
Published in:Angewandte Chemie 2021-11, Vol.133 (46), p.24855-24863
Main Authors: Rothfelder, Robin, Streitferdt, Verena, Lennert, Ulrich, Cammarata, Jose, Scott, Daniel J., Zeitler, Kirsten, Gschwind, Ruth M., Wolf, Robert
Format: Article
Language:English
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Summary:Detailed 31 P{ 1 H} NMR spectroscopic investigations provide deeper insight into the complex, multi‐step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P 4 ). Specifically, these studies have identified a number of previously unrecognized side products, which arise from an unexpected non‐innocent behavior of the commonly employed terminal reductant Et 3 N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy) 2 ][PF 6 ] (dtbbpy=4,4′‐di‐ tert ‐butyl‐2,2′‐bipyridine) and 3DPAFIPN. Inspired by the observation of PH 3 as a minor intermediate, we have developed the first catalytic procedure for the arylation of this key industrial compound. Similar to P 4 arylation, this method affords valuable triarylphosphines or tetraarylphosphonium salts depending on the steric profile of the aryl substituents.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202110619