Classically tetraaryl diphosphanes have been synthesized through Wurtz-type reductive coupling of halophosphanes RPX or more recently, through the dehydrocoupling of phosphines RPH. Catalytic variants of the dehydrocoupling reaction have been reported, but are limited to RPH compounds. Using PEt as a catalyst, we now show that TipPBr (Tip = 2,4,6-PrCH) is selectively coupled to give the dibromodiphosphane (TipPBr) (1), a compound not accessible using classic Mg reduction. Surprisingly, when using DipPBr (Dip = 2,6-PrCH) in the PEt catalysed reductive coupling the diphosphene (PDip) (2) with a PP double was formed selectively. In benzene solutions (PDip) has a half life time of 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 PhPCl and MesPX (X = Cl, Br) are efficiently coupled using 10 mol% of PEt to give (PhP) and (MesP), respectively. Control experiments show that [BrPEt]Br is a potential oxidation product in the catalytic cycle, which can be debrominated by Zn dust as a sacrificial reductant.
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