A straightforward access to ruthenium-coordinated fluorophosphines from phosphorous oxyacids

The transformation of phosphorous oxyacids into the corresponding fluorophosphines was mediated by [CpRu(PPh3)2Cl] under mild reaction conditions using a soft deoxofluorinating agent. The reaction is selective, proceeds with high yields and can be extended to a wide range of phosphorous oxyacids once coordinated to the ruthenium synthon {CpRu(PPh3)2}+ as their hydroxyphosphine tautomer. Deoxofluorination of phenylphosphinic acid was also mediated by [CpRRu(CH3CN)3]PF6, where CpR: Cp = C5H5, Cp* = C5Me5, and {?6-(p-cymene)Ru(µ-Cl)Cl}2.. X-ray single crystal structures of the two new derivatives, [CpRu(PPh3)2{PhP(OH)2}]CF3SO3 and [?6-(p-cymene)RuCl2?PhP(OH)2}] have been determined.