1732-66-7Relevant articles and documents
Alkyne 1,1-Hydroboration to a Reactive Frustrated P/B-H Lewis Pair
?koch, Karel,Daniliuc, Constantin G.,Kehr, Gerald,Erker, Gerhard
, p. 6757 - 6763 (2021)
The Mes2P-C≡C-SiMe3 alkyne reacts with the borane H2B-Fmes by means of a rare 1,1-hydroboration reaction to give an unsaturated C2-bridged frustrated P/B-H Lewis pair. Most of its reactions are determined by the presence of the B-H functionality at the FLP function and the activated connecting carbon-carbon double bond. It reduces carbon monoxide to the formyl stage. With nitriles it reacts in an extraordinary way: it undergoes a reaction sequence that eventually results in the formation of a P-substituted dihydro-1,2-azaborole derivative. Several similar examples were found. In one case a P-ylide was isolated that was related to an intermediate of the reaction sequence. It subsequently opened in an alternative way to give an alkenyl borane product.
Reactions of activated organonickel σ-complexes with elemental (white) phosphorus
Yakhvarov,Kvashennikova,Sinyashin
, (2013)
The reactivity of organonickel σ-complexes of the type [NiBr(Ar)(bpy)] (Ar is 2,4,6-tri-methylphenyl (Mes) or 2,4,6-triisopropylphenyl (Tipp); bpy is 2,2′-bipyridine) toward elemental (white) phosphorus was studied. For the reaction to occur, the complexe
Photocatalytic Arylation of P4 and PH3: Reaction Development Through Mechanistic Insight
Cammarata, Jose,Gschwind, Ruth M.,Lennert, Ulrich,Rothfelder, Robin,Scott, Daniel J.,Streitferdt, Verena,Wolf, Robert,Zeitler, Kirsten
supporting information, p. 24650 - 24658 (2021/10/14)
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.