η5-Pentamethylcyclopentadienylruthenium(II) complexes containing η6-co-ordinated dipeptides with aromatic side chains
摘要:
The eta(6)-co-ordinated amino acid complexes [RU(eta(5)-C(5)Me(5))(eta(6)-HaaOH)][CF3SO3] [HaaOH = L-HPheOH (phenylalanine) or L-HTrpOH (tryptophan)] were prepared by reaction of [Ru(eta(5)-C(5)Me(5))(MeCN)(3)][CF3SO3] with the relevant amino acid in tetrahydrofuran. Dipeptide complexes of the type [{Ru(eta(5)-C(3)Me(5))}(2)(mu-eta(6):eta(6)-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(eta(5)-C(5)Me(5))}(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(eta(5)-C(5)Me(5)){eta(6)-cyclo(-Phe-Phe-)}]Cl from [Ru(eta(5)-C(5)Me(5))(eta(6)-L-HPhe-OMe)]Cl by the carbodiimide method. A crystal structure analysis was carried out for[{Ru(eta(5)-C(5)Me(5))}(2){cyclo(-Phe-Phe-)}][CF3SO3](2).