A variety of diphenyldiphosphinites have been prepared in a very stable form as Pt II or PdII complexes by adding diols to a solution containing cis-[MCl2(PPh2Cl)2](M=PtorPd) preformed in situ from cis-[MCl2(1,5-COD)] (M = Pt; M = Pd) and PPh2Cl. This synthetic pathway can be used for diphos- phinites derived from aliphatic 1,2 and 1,3 diols and also from the aromatic catechol. Besides the P−O bond, it is also shown here that the P−N bond can also be formed via nucleophilic attack of an amine group on coordinated PPh2Cl in the pres- ence of a base resulting in some AMPP and BAMP complexes of Pt and Pd . The X-ray crystal structures of the [cis- cyclohexanediyl bis(diphenylphosphinite)]platinum dich ide, of the AMPP palladium complex from (1R,2S)-(−)-n phedrine and of the BAMP palladium complex [P,P phenyl-1,2-cyclohexanediylbis(imino)bisphosphan palladium dichloride have been determined. The chem and optical stabilities of many complexes in solution h been monitored by 31P NMR spectroscopy.
The construction of P-O/P-N ligands on platinum and palladium
BERGAMINI, Paola;BERTOLASI, Valerio;
2004
Abstract
A variety of diphenyldiphosphinites have been prepared in a very stable form as Pt II or PdII complexes by adding diols to a solution containing cis-[MCl2(PPh2Cl)2](M=PtorPd) preformed in situ from cis-[MCl2(1,5-COD)] (M = Pt; M = Pd) and PPh2Cl. This synthetic pathway can be used for diphos- phinites derived from aliphatic 1,2 and 1,3 diols and also from the aromatic catechol. Besides the P−O bond, it is also shown here that the P−N bond can also be formed via nucleophilic attack of an amine group on coordinated PPh2Cl in the pres- ence of a base resulting in some AMPP and BAMP complexes of Pt and Pd . The X-ray crystal structures of the [cis- cyclohexanediyl bis(diphenylphosphinite)]platinum dich ide, of the AMPP palladium complex from (1R,2S)-(−)-n phedrine and of the BAMP palladium complex [P,P phenyl-1,2-cyclohexanediylbis(imino)bisphosphan palladium dichloride have been determined. The chem and optical stabilities of many complexes in solution h been monitored by 31P NMR spectroscopy.I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
