9-BBN and chloride catalyzed reduction of chlorophosphines to phosphines and diphosphines

Abstract

The commercially available Lewis acid, 9-BBN and Lewis basic [Et4N]Cl are used as catalysts for the reduction of chlorophosphines R2PCl in the presence of phenylsilane. Aryl-chlorophosphines afford primarily diphosphines (P2R4)...

A Copper(I) Platform for One-Pot P–H Bond Formation and Hydrophosphination of Heterocumulenes

“…Despite the challenges associated with handling these compounds, a number of routes to primary and secondary phosphines have been reported, driven by their utility in synthesis. − These approaches provide access to a wide library of primary and secondary phosphines but still rely on their isolation before synthetic utilization and often necessitate the handling of toxic or highly reactive compounds such as tin derivatives and alanes. The action of silanes on phosphorus­(V) esters catalyzed by B­(C 6 F 5 ) 3 was reported to generate a small range of phosphines, including PH 3 , but suffered from long reaction times and, in some cases, limited conversion .…”

Reversible P–P bond cleavage at an iridium(iii) metal centre

“…By contrast, the coordination chemistry of P-based compounds such as terminal/bridging phosphides (PR 2 − ) 1 and, to a lesser extent, diphosphanes (R 2 P–PR 2 ), 2 have witnessed relatively few studies. In spite of this, there is a growing interest 3 in new synthetic routes to R 2 P–PR 2 compounds given also the importance of P–P bonded species in organophosphorus chemistry. Metal bound phosphide ligands can undergo P–P radical coupling leading to dimeric products, 4 in a few instances this process is reversible (Chart 1).…”

“…Various groups 2,3,6,9–12 have reported the synthesis and reactivity of several types of R 2 P–PR 2 , with acyclic variants being most common. We reasoned a “rigid” R 2 P–PR 2 would reduce P–P bond rotation/dissociation yet still function as a bridging ligand.…”

Indium-Catalyzed Reductive Coupling Enabled Efficient Synthesis of Acylphosphine Oxides and Diphosphines

“…Although this route is straightforward, the use of at least 4 equiv of the metal sodium poses significant safety problems. For the construction of P–P bonds, previous methods mainly focused on homodehydrocoupling of phosphines (R 2 PH) that are obtained from the reduction of R 2 PCl using stoichiometric reductants . Therefore, the search for more efficient, safe, and easy-to-handle methods for P–C­(O) and P–P bond formation is highly desirable from the perspective of both academic research and industrial application.…”