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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., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

New iron complexes [Cp*FeL] - (1-σ and 1-π, Cp*=C 5 Me 5 ) containing the chelating phosphinine ligand 2-(2'-pyridyl)-4,6-diphenylphosphinine (L) have been prepared, and found to undergo facile reaction with CO 2 under ambient conditions. The outcome of this reaction depends on the coordination mode of the versatile ligand L. Interaction of CO 2 with the isomer 1-π, in which L binds to Fe through the phosphinine moiety in an η 5 fashion, leads to the formation of 3-π, in which CO 2 has undergone electrophilic addition to the phosphinine group. In contrast, interaction with 1-σ-in which L acts as a σ-chelating [P,N] ligand-leads to product 3-σ in which one C=O bond has been completely broken. Such CO 2 cleavage reactions are extremely rare for late 3d metals, and this represents the first such example mediated by a single Fe centre., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)