η5-Pentamethylcyclopentadienylruthenium(II) complexes containing η6-co-ordinated dipeptides with aromatic side chains

Abstract
The η6-co-ordinated amino acid complexes [Ru(η5-C5Me5)(η6-HaaOH)][CF3SO3][HaaOH =L-HPheOH (phenylalanine) or L-HTrpOH (tryptophan)] were prepared by reaction of [Ru(η5-C5Me5)(MeCN)3][CF3SO3] with the relevant amino acid in tetrahydrofuran. Dipeptide complexes of the type [{Ru(η5-C5Me5)}2(µ-η6 : η6-pep)][CF3SO3]2[pep = HPhe-PheOH, cyclo(-Phe-Phe-), HTrp-TrpOH, or cyclo (-Trp-Trp-)] may be obtained under analogous conditions. Ultraviolet irradiation of [{Ru(η5-C5Me5)}2{cyclo(-Phe-Phe-)}][CF3SO3]2 leads to photochemical release of cyclo(-Phe-Phe-) in quantitative yield. The feasibility of peptide synthesis from individual amino acid complexes was demonstrated by the preparation of [Ru(η5-C5Me5){η6-cyclo(-Phe-Phe-)}]Cl from [Ru(η5-C5Me5)(η6-L-HPhe-OMe)]Cl by the carbodiimide method. A crystal structure analysis was carried out for [{Ru(η5-C5Me5)}2{cyclo(-Phe-Phe-)}][CF3SO3]2.

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