METAL COMPLEXES WITH ALLYLANILINES. IV. SYNTHESIS AND REACTIVITY OF RHODIUM(I) COMPLEXES WITH 2-ALLYLANILINE AND N-ALLYLANILINE

Article abstract of DOI:10.1016/S0022-328X(00)93823-3

The reaction of 2-allylaniline (2aa) with 2 (I) in toluene or benzene at room temperature affords the dimer 2 (II) in which the ligand acts as bidentate, being coordinated to the metal through the N atom and the olefinic group.II in CH2Cl2, isomerizes 2aa to trans-2-propenylaniline.This reaction goes also catalytically.Heating of II in benzene affords 2-methyl-indoline.N-Allylaniline (naa) reacts with I to give the deep violet diamagnetic complex Rh2Cl2(naa)3 (III), which is converted slowly into 2.When III is heated with an excess of naa, the ligand is catalytically transformed into propene, azobenzene, N-n-propylaniline, N-i-propylaniline, N-allylideneaniline and aniline, as the more abundant products.Moreover, III reacts with diphenylacetylene to afford 2,5-dihydro-1,2,3-triphenyl-4-methyl-pyrrole.The reaction of III with methylacetylene follows a more complex path, and products of dimerization and trimerization of the alkyne have been isolated.Carbon dioxide influences the oligomerization reaction.