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Photocatalytic Arylation of P4 and PH3 : Reaction Development Through Mechanistic Insight.
Robin Rothfelder1, Verena Streitferdt2, Ulrich Lennert1
1Institute of Inorganic Chemistry, University of Regensburg, 93040, Regensburg, Germany.
Angewandte Chemie (International Ed. in English)
|September 2, 2021
Summary
Phosphorus NMR studies reveal side products in photocatalytic arylation due to reductant behavior. This led to a new catalytic method for arylating phosphine (PH3), yielding valuable phosphine products.
Area of Science:
- Organometallic Chemistry
- Photocatalysis
- Spectroscopy
Background:
- Photocatalytic arylation of white phosphorus (P4) is a recent advancement.
- Understanding reaction mechanisms is crucial for optimizing catalyst performance.
- Triethylamine (Et3N) is a common reductant in these reactions.
Purpose of the Study:
- To elucidate the complex mechanisms of P4 photocatalytic arylation.
- To identify previously unrecognized side products and their origins.
- To develop a catalytic method for phosphine (PH3) arylation.
Main Methods:
- Detailed 31P{1H} NMR spectroscopy was employed.
- Investigation of photocatalytic arylation reactions.
- Development of a novel catalytic arylation procedure.
Main Results:
- Identified side products arising from the non-innocent behavior of Et3N.
- Explained performance discrepancies between catalysts [Ir(dtbbpy)(ppy)2][PF6] and 3DPAFIPN.
- Developed the first catalytic arylation method for PH3, yielding triarylphosphines or tetraarylphosphonium salts.
Conclusions:
- The reductant Et3N plays a complex role in P4 arylation, leading to side products.
- Catalyst performance is influenced by the rate of side product formation.
- A new catalytic route for PH3 arylation has been established, expanding synthetic possibilities.
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