Transition-metal-Carbon Bonds. Part 46. Cyclopalladation and Cycloplatination of N-Alkyl-N-Nitrosoanilines

Article abstract of DOI:10.1039/DT9800002282

N-Methyl-N-nitrosobenzylamine (O) is not cyclo-(ortho-)palladated by Na2 but gives a complex of type .In contrast N-methyl-N-nitrosoaniline is readily ortho palladated to give the chlorobridged complex (4a).This was converted into a mononuclear acetylacetonate (5a) and into species , L=PPh3 (crystal structure determined), PMe2Ph, or pyridine, (6a), (6b), or (6c) respectively.With two moles of PPh3 per palladium the Pd-NO bond is broken giving the ?-aryl species Cl(PPh3)2> (7a), the crystal structure of which has also been determined.With 1,2-bis(diphenylphosphino)ethane (dppe), (4a) gives the ion isolated as its tetraphenylborate salt (8a).Some palladated derivatives of N-ethyl-N-nitrosoaniline and (4-methoxy)-N-methyl-N-nitrosoaniline were made similarly.With K2 N-methyl-N-nitrosoaniline gives a red material which was not obtained pure but which gave a mononuclear acetylacetonate (5c) and bis-phosphine complex Cl(PPh3)2> (7d) analogous to the palladium complex.N-Ethyl-N-nitrosoaniline reacted similarly.Crystals of (6a) are triclinic, space group P1, with a = 9.990(2), b = 15.195(3), c = 9.276(2) Angstroem, α = 104.05(2), β = 97.92(2), γ = 89.47(2) deg , and Z = 2.Those of 7a are monoclinic, space group P2₁/c with a = 12.047(2), b = 21.794(4), c = 16.402(2) Angstroem, β = 108.54(1) deg, and Z = 4.Both compounds crystallise with a molecule of CH2Cl2.Least-squares refinements gave final R values of 0.089 for (6a) and 0.083 for (7a).

Full text of DOI:10.1039/DT9800002282

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