Facile interconversions between diastereomers of chloro-bridged palladium(II) dimers of orthometallated (+/-)-dimethyl[1-(1-naphthyl)ethyl]amine

The important chloro-bridged dipalladium(Il) resolving agents (RR)- and (S,S)-cis-di-mu-chlorobis[1-[1-(dimethylamino)-ethyl]-2- naphthalenyl-C,N]dipalladium, (R,R)- and (S,S)-cis-1, undergo facile rearrangements into unequal mixtures of cis and trans diastereomers upon dissolution in chloroform or dichloromethane, although concentration of the solution in each case affords in high yield the pure cis diastereomer of the dinuclear metal complex as the corresponding mono-solvate in a typical second-order asymmetric transformation. When equimolar solutions of(R,R)-cis- and (S,S)-cis-1-CH2Cl2 in dichloro-methane are mixed together, however, an equilibrium is rapidly established between the cis and trans diastereomers of the (R*,R*)-(+/-) and (R*,S*) forms of 1 and from which solution configurationally homogeneous (R*,S*)-trans-1-CH2Cl2 crystallizes in high yield by second-order asymmetric transformation. The crystal and molecular structures of (R,R)-cis-1-CH2Cl2 and (R*,S*)-trans-1-CH2Cl2 have been determined. The optical purities of the individual enantiomers of (R*,R*)-(+/-)-1-CH2Cl2 have been determined by reaction with (1R,2S,5R)-menthyldiphenylphosphine or (1S, 2S, 5R)-neomethyldiphenylphosphine in chloroform-d(1) and analysis of the P-31(H-1) NMR spectra of the resulting solutions of the corresponding bridge-split palladium(II)-phosphine epimers. (C) 1997 Elsevier Science Ltd.