Photocatalytic Arylation of P4 and PH3: Reaction Development Through Mechanistic Insight

Robin Rothfelder, Verena Streitferdt, Ulrich Lennert, Jose Cammarata, Daniel J. Scott, Kirsten Zeitler, Ruth Gschwind, Robert Wolf

Research output: Contribution to journalArticlepeer-review

Abstract

Detailed 31P{1H} NMR spectroscopic investigations provide deeper insight into the complex, multi-step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P4). 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 Et3N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy)2][PF6] (dtbbpy=4,4′-di-tert-butyl-2,2′-bipyridine) and 3DPAFIPN. Inspired by the observation of PH3 as a minor intermediate, we have developed the first catalytic procedure for the arylation of this key industrial compound. Similar to P4 arylation, this method affords valuable triarylphosphines or tetraarylphosphonium salts depending on the steric profile of the aryl substituents.
Original languageEnglish
Pages (from-to)24650-24658
JournalAngewandte Chemie - International Edition
Volume60
Issue number46
Early online date11 Oct 2021
DOIs
Publication statusPublished - 8 Nov 2021

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