Cyclometalation of Secondary Benzyl Amines by Ruthenium(II) Complexes
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文摘
The cyclometalation of chiral secondary amines through ortho-metalation of an aryl group occurredreadily with [(6-benzene)RuCl2]2 in acetonitrile. Reasonable to good yields of the expected cationicproducts of the form [(6-benzene)Ru(N-C)(NCMe)](PF6), in which N-C represents the cyclometalatedligands, were obtained with bis-(R)-phenylethylamine, bis-(R)-1-naphthylethylamine, and (2R,5R)-2,5-diphenylpyrrolidine. Variable proportions of the expected four diastereoisomers were found according toNMR studies. The stereochemistry of complexes was investigated by 2D NMR in solution and by X-raydiffraction of single crystals. The (S) configuration at the metal was generally associated with a conformation of the metallacycle, and conversely, the (R) configuration with the conformation.

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