Synthesis and coordination chemistry of enantiopure t-BuMeP(O)H.

Both enantiomers of the optically pure Secondary Phosphine Oxide (SPO) t-BuMeP(O)H (1) have been obtained by deboronation of phosphinous acid-borane t-BuMeP(O)H center dot BH3 (3) with HBF4 followed by hydrolysis of the intermediate adduct t-BuMeP(O)H center dot BF3 (1 center dot BF3), which has been isolated and crystallographically characterised. Complexes [MCl(COD)(kappa P-(R)-1)] (M = Ir, Rh; 4 and 7 respectively) have been detected in solution but could not be isolated while trans-[RhCl(CO)(kappa P-(S)-1)(2)] (9) has been successfully obtained in good yield. Gold complex [AuCl(kappa P-(S)-1)] (10) has been prepared and its crystal structure shows the presence of aurophilic interactions. Three new ruthenium complexes ([RuCl2(eta(6)-p-cymene)(kappa P-(R)-1)], 12), ([RuCl2(CO)(3)(kappa O-(S)-1)], 13) and trans-([RuCl2(CO)(2)(kappa P-(S)-1)(2)], 14) have been synthesised and fully characterised, including the crystal structure of 12. Four palladium coordination compounds have been prepared: trans-[PdCl2(kappa P-(S)-1)(2)] (trans-15), [Pd(mu-Cl)(kappa P-(S)-1)(2)](2) (16 center dot OH and 16 center dot BF2) and [Pd(mu-OAc)(kappa P-(S)-1)(2)] (17) and the crystal structure of complex 16 center dot OH proves the pseudobidentate coordination of the two molecules of 1. Three organometallic allylpalladium complexes have been prepared namely [Pd(eta(3)-Ph2C2H3)Cl(kappa P-(S)-1)] (18) and [Pd(eta(3)-Ph2C2H3)(kappa P-(S)-1)(2)] (19 center dot OH and 19 center dot BF2). The crystal structure of 19 center dot BF2 constitutes the first allylpalladium-SPO complex reported to date.