SYNTHESIS, RESOLUTION AND REACTIONS OF (+ -)-(2-AMINO-PHENYL)METHYLPHENYLPHOSPHINE - CRYSTAL AND MOLECULAR-STRUCTURE OF (R-ASTERISK, R-ASTERISK, S-ASTERISK, YLPHENYL-PHOSPHINO)PHENYL]AMINO)PROPANE)NICKEL(II) PERCHLORATE/

Asymmetric bidentate (+/-)-(2-aminophenyl)methylphenylphosphine has be en prepared in 80% yield from (2-aminophenyl)diphenylphosphine via the secondary phosphine (+/-)-(2-aminophenyl)phenylphosphine. The chiral tertiary phosphine has been resolved by the method of metal complexati on via the separation by fractional crystallisation of a pair of inter nally diasteromeric palladium(II) complexes containing the racemic lig and and (S)-[1-(1-ethyl)naphthyl]dimethylamine. The optically pure ant ipodes of the phosphine have alpha +/- 160-degrees (589 nm, CH2Cl2). A number of square-planar bis(bidentate ligand) complexes of bivalent n ickel, palladium and platinum containing the various forms of the liga nd have been prepared and their solution behaviour studied by H-1 and P-31-{H-1} NMR spectroscopy. Monodeprotonation of the co-ordinated ami no groups in the complexes has also been achieved by reaction with any hydrous sodium carbonate in acetone. The palladium(II) and platinum(II ) complexes form cis diasteromers exclusively, whereas trans diastereo mers were observed for the nickel(II) analogoues. Furthermore, most of the complexes are kinetically labile. Reaction of (+/-)-(2-aminopheny l)methylphenylphosphine with n-butyllithium and N,N,N',N'-tetramethyle thylenediamine in tetrahydrofuran followed by the addition of 1,3-bis( p-tolysulfonyloxy)propane gave the quadridentate ligand (R,R*)- and i s{[2-(methylphenylphosphino)phenyl]amino}propane. The (R,R*) and (R*, S) forms of the quadridentate ligand have been separated by complexat ion to nickel(II). The structure of the nickel(II) complex containing the (R,R*) form of the quadridentate ligand, viz. hylphenylphosphino) phenyl]amino}propane)nickel(II) perchlorate, has been determined by X- ray crystallography.