Optically active cyclopalladated derivatives of arylimines.: Crystal structures of (+)-[{Pd[p-MeOC6H3CH=NCH2-(1S,2R,5S)-CHCH2CH2CHC(Me)2CHCH2](μ-X)}2] (X = Cl or Br), (+)-[Pd{p-MeOC6H3CH=NCH2-(1S,2R,5S)-CHCH2-CH2CHC(Me)2CHCH2}Cl(PPh3)] and (+)-[{Pd[p-Me-OC6H3CH=NCH2-(1S,2R,5S)-CHCH2CH2CHC(Me)2CHCH2]Cl}2-{Fe(η5-C5H4PPh2)2}]

4-Methoxybenzaldehyde reacted with(-)-(1S,2R,5S)-2-aminomethyl-6,6-dimethylbicyclo[3.1.1]heptane in benzene to give the new chiral arylimine p-MeOC6H4CH=NCH2-(1S,2R,5S)-CHCH2CH2CHC(CH3)(2)CHCH2 [(-)-1]. Cyclopalladation of the imine with Pd(O2CMe)(2) in MeCO2H, followed by treatment with LiCl, LiBr or KI, gave the corresponding di-mu-halide-bridged organometallics (+)-[{Pd[p-MeOC6H3CH=NCH2-(1S,2R,5S)-CHCH2CH2CHC(Me)(2)CHCH2](mu-X)}(2)] [X = Cl (+)-1a, Br (+)-1b or I (+)-1c]. Subsequent treatment of these compounds with triphenylphosphine, pyridine (py) or 1,1'-bis(diphenylphosphino)ferrocene (dppf) in acetone yielded the corresponding cyclopalladated derivatives (+)-[Pd{p-MeOC6H3CH=NCH2-(1S,2R,5S)-CHCH2CH2CHC(Me)(2)CHCH2}X(PPh3)] [X = Cl(+)-2a, Br (+)-2b or I(+)-2c], (+)-[Pd{p-MeOC6H3CH=NCH2-(1S, 2R,5S)-CHCH2CH2CHC(CH3)(2)CHCH2}X(py)] [X = Cl (+)-3a, Br (+)-3b or I (+) 3c] and (+)-[{Pd[p-MeOC6H3CH=NCH2-(1S,2R,5S)-CHCH2CH2CHC(Me)(2)CHCH2)]X}(2)(dppf)] [X = Cl (+)-4a, Br (+)-4b or I (+)-4c], which have been characterized by NMR and mass spectrometry, optical rotation and elemental analysis. The crystal structures of(+)-1a, (+)-1b, (+)-2a and (+)-4b . CH2Cl2 have been determined.