Effectof the Phosphine Steric and Electronic Profileon the Rh-Promoted Dehydrocoupling of Phosphine–Boranes

摘要

The electronic and steric effects in the stoichiometric dehydrocoupling of secondary and primary phosphine–boranes H3B·PR2H [R = 3,5-(CF3)2C6H3; p-(CF3)C6H4; p-(OMe)C6H4; adamantyl, Ad] and H3B·PCyH2 to form the metal-bound linear diboraphosphines H3B·PR2BH2·PR₂H and H₃B·PRHBH₂·PRH₂, respectively, are reported. Reaction of [Rh(L)(η⁶-FC₆H₅)][BAr^F₄] [L = Ph₂P(CH₂)₃PPh₂, Ar^F = 3,5-(CF₃)₂C₆H₃] with 2 equiv of H₃B·PR₂H affords [Rh(L)(H)(σ,η-PR₂BH₃)(η¹-H₃B·PR₂H)][BAr^F₄]. These complexes undergo dehydrocoupling to give the diboraphosphine complexes [Rh(L)(H)(σ,η²-PR₂·BH₂PR₂·BH₃)][BAr^F₄]. With electron-withdrawing groups on the phosphine–borane there is the parallel formation of the products of B–P cleavage, [Rh(L)(PR₂H)₂][BAr^F₄], while with electron-donating groups no parallel product is formed. For the bulky, electron rich, H₃B·P(Ad)₂H no dehydrocoupling is observed, but an intermediate Rh(I) σ phosphine–borane complex is formed, [Rh(L){η²-H₃B·P(Ad)₂H}][BAr^F₄], that undergoes B–P bond cleavage to give [Rh(L){η¹-H₃B·P(Ad)₂H}{P(Ad)₂H}][BAr^F₄]. The relative rates of dehydrocoupling of H₃B·PR₂H (R = aryl) show that increasingly electron-withdrawing substituents result in faster dehydrocoupling, but also suffer from the formation of the parallel product resulting from P–B bond cleavage. H₃B·PCyH₂ undergoes a similar dehydrocoupling process, and gives a mixture of stereoisomers of the resulting metal-bounddiboraphosphine that arise from activation of the prochiral P–Hbonds, with one stereoisomer favored. This diastereomeric mixturemay also be biased by use of a chiral phosphine ligand. The selectivityand efficiencies of resulting catalytic dehydrocoupling processesare also briefly discussed.