| Abstract
| - The cyclometalation of chiral and achiral primary amines occurred readily with Ru(II), Rh(III), andIr(III) derivatives. Thus, the metalation of (R)-1-phenylethylamine by [(η6-benzene)RuCl2]2, [(η5-Cp*)RhCl2]2, and [(η5-Cp*)IrCl2]2 was studied. Good yields of the expected cationic products in which thephenyl group was ortho-metalated were obtained for the rhodium and the ruthenium derivatives, whereasa mixture of products was formed in the case of the iridium complex. Benzylamine, (R)-1-phenylpropylamine, (R)-1-(1-naphthyl)ethylamine, and (R)-1-aminotetraline afforded also the cycloruthenationproducts whose general formula is [(η6-benzene)Ru(N−C)(NCMe)]PF6 where N−C represents the ortho-metalated ligands. Substitution of the acetonitrile ligand by PMe2Ph occurred readily on the rutheniumcomplexes, affording stable compounds that were characterized by X-ray diffraction studies on singlecrystals, thus ascertaining the existence of the cycloruthenated five-membered rings. Accurate analysesof the structure of the complexes were implemented in solution and in the solid state. The (S) configurationat the metal was usually associated with a δ conformation of the metallacycle, and conversely, the (R)configuration with the λ conformation. The study of the conformation of the five-membered rings revealedthat the orientation of the NH2 group is such that one NH unit is oriented toward the η6-benzene ring(roughly parallel to the Ru−centroid benzene vector), whereas the second NH is parallel to the Ru−Lbond, L = NCMe or PMe2Ph.
- The cyclometalation of primary amines by Ru(II), Rh(III), and Ir(III) was achieved under mild conditions while treating primary amines with either [(η6-C6H6)RuCl(μ-Cl)]2 or [(η5-C5Me5)MCl(μ-Cl)]2, M = Rh, Ir.
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