Journal
ORGANOMETALLICS
Volume 26, Issue 8, Pages 1856-1867Publisher
AMER CHEMICAL SOC
DOI: 10.1021/om060973t
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The cyclometalation of chiral and achiral primary amines occurred readily with Ru(II), Rh(III), and Ir(III) derivatives. Thus, the metalation of (R)-1-phenylethylamine by [(eta(6)-benzene)RuCl2](2), [(eta(5)-Cp*)RhCl2](2), and [(eta(5)-Cp*)IrCl2](2) was studied. Good yields of the expected cationic products in which the phenyl group was ortho-metalated were obtained for the rhodium and the ruthenium derivatives, whereas a 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 cycloruthenation products whose general formula is [(eta(6)-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 ruthenium complexes, affording stable compounds that were characterized by X-ray diffraction studies on single crystals, thus ascertaining the existence of the cycloruthenated five-membered rings. Accurate analyses of the structure of the complexes were implemented in solution and in the solid state. The (S) configuration at the metal was usually associated with a delta conformation of the metallacycle, and conversely, the (R) configuration with the lambda conformation. The study of the conformation of the five-membered rings revealed that the orientation of the NH2 group is such that one NH unit is oriented toward the eta(6)-benzene ring (roughly parallel to the Ru-centroid benzene vector), whereas the second NH is parallel to the Ru-L bond, L = NCMe or PMe2Ph.
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