The rational, sequential synthesis of two hetero-bimetallic derivatives of the amino acid phenylalanine and one thymine (T) peptide nucleic acid (PNA) monomer is reported. Ferrocene carboxylic acid and (η-ethene)bis(triphenylphosphine)platinum(0) were successfully reacted with propargylamide amino acid (1a and 1b) or a T PNA monomer derivative (6) to give the expected three bimetallic compounds 4a, 4b and 9 in good yield. An enzymatic route using cross-linked enzyme crystals (CLEC) of subtilopeptidase A in organic solvents gave the ferrocene carboxylate phenylalanine propargylamide precursor (Fc-CO-Phe-NH-CH2-CCH, 3a) in comparable yield and purity to the traditional deprotection-peptide coupling sequence. 31P NMR spectra of these bioorganometallics showed two doublets with 195Pt satellites corresponding to two chemically different 31P atoms. Interestingly, in the case of the T PNA monomer derivative 9, these signals were also doubled in a 60 : 40 ratio as a consequence of the existence of two slowly interconverting isomers in solution. Furthermore, the single-crystal X-ray structures of 3a and the hetero-bimetallic phenylalanine derivative 4b were determined, showing the presence of the two organometallics moieties separated by ca. 8.5 Å in 4b as well as illustrating the stability of such compounds.
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