Phosphine-catalysed reductive coupling of dihalophosphanes

Abstract

Classically tetraaryl diphosphanes have been synthesized through Wurtz-type reductive coupling of halophosphanes R₂PX or more recently, through the dehydrocoupling of phosphines R₂PH. Catalytic variants of the dehydrocoupling reaction have been reported, but are limited to R₂PH compounds. Using PEt₃ as a catalyst, we now show that TipPBr₂ (Tip = 2,4,6-iPr₃C₆H₂) is selectively coupled to give the dibromodiphosphane (TipPBr)₂ (1), a compound not accessible using classic Mg reduction. Surprisingly, when using DipPBr₂ (Dip = 2,6-iPr₃C₆H₃) in the PEt₃ catalysed reductive coupling the diphosphene (PDip)₂ (2) with a PP double was formed selectively. In benzene solutions (PDip)₂ has a half life time of ca. 28 days and can be utilized with NHCs to access NHC-phosphinidene adducts. To show that this protocol is more widely applicable, we show that Ph₂PCl and Mes₂PX (X = Cl, Br) are efficiently coupled using 10 mol% of PEt₃ to give (Ph₂P)₂ and (Mes₂P)₂, respectively. Control experiments show that [BrPEt₃]Br is a potential oxidation product in the catalytic cycle, which can be debrominated by Zn dust as a sacrificial reductant.