ORTHOMETALLATED PRIMARY AMINES .3. THE FIRST ORTHOPALLADATION OF A PRIMARY NITROBENZYLAMINE - SYNTHESIS OF CHIRAL CYCLOPALLADATED COMPLEXES DERIVED FROM (S)-ALPHA-METHYL-4-NITROBENZYLAMINE

By refluxing a mixture of (S)-alpha-methyl-4-nitrobenzylamine and Pd(O2CMe)(2) (1:1) in acetone. complexes (S,S)-[{Pd[C6H3{CH(Me)NH2}-2-NO2-5](mu-X)}(2)] (X = MeCO2 1a or Cl 1b) are obtained. Complex 1b can also be obtained by treating (S)-alpha-methyl-4-nitrobenzylamine hydrochloride with Pd(O2CMe)(2) (1:1) in acetone. These complexes are the first orthometallated complexes containing a primary amine with an electron-withdrawing group in the benzene ring. Complex la reacted with an excess of NaBr or NaI to give (S,S)-[{Pd[C6H3{CH(Me)NH2}-2-NO2-5](mu-X)}2] (X = Br 1c or I 1d). Triphenylphosphine reacted with 1b or 1c to give (S)-[Pd{C6H3[CH(Me)NH2]-2-NO2-5}X(PPh3)] (X = Cl 2a or Br 2b). The reaction of complex 1b with AgClO4 (1:1) and an excess of pyridine (py) save (S)-[Pd{C6H3[CH(Me)NH2]-2-NO2-5}(py)(2)]ClO4 3. Complex 1c reacted with 3 equivalents of RC=CR (R = CO2Me) to give a tri-insertion reaction product. the crystal structure of which has been determined: space group P2(1)2(1)2(1), a = 11.0969(14), b = 17.197(2). c = 19.604(3) Angstrom. R(F) = 0.041. The planar co-ordination at palladium is not significantly disturbed by a short contact of 2.600 Angstrom to the C atom of a CO2Me group. A cationic derivative of this complex has also been prepared.