Template synthesis of chiral vicinal diphosphinites as their Pt-II and Pd-II complexes

The metal-templated synthesis of a few examples of vicinal diphenylphosphinites is accomplished when the corresponding vicinal diols react with the diphenylchlorophosphane complexes cis-[MCl2(PPh2Cl)2] (M = Pt, Pd) in anhydrous THF. This process is proposed as a new synthetic route for PtII and PdII complexes of the new ligands 1,2-bis(diphenylphosphinito)butane, 2,3-bis(diphenylphosphinito)butane, and 2,3-bis(diphenylphosphinito)diisopropyl-L-tartrate, containing seven-membered chelate rings including stereogenic carbons. The new chiral phosphane-phosphinite (R)-3-(diphenylphosphanyl)-2-(diphenylphosphinito)propanol has also been obtained as a PtII six-membered chelate. The X-ray crystal structure of some of the described complexes and NMR evidence of the possibility of removing the ligands from the metal are reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)