Synthesis of hybrid transition-metalloproteins viathiol-selective covalent anchoring of Rh-phosphine and Ru-phenanthroline complexesElectronic supplementary information (ESI) available: Details of protein production, MS spectra of conjugates and catalysis procedures. See DOI: 10.1039/c0dt00239a

The preparation of hybrid transition metalloproteins by thiol-selective incorporation of organometallic rhodium- and ruthenium complexes is described. Phosphine ligands and two rhodium-diphosphine complexes bearing a carboxylic acid group were coupled to the cysteine of PYP R52G, yielding a metalloenzyme active in the rhodium catalyzed hydrogenation of dimethyl itaconate. The successful coupling was shown by 31P NMR spectroscopy and ESI mass spectroscopy. In addition wild-type PYP (PYP WT), PYP R52G and ALBP were successfully modified with a (η6-arene) ruthenium(ii) phenanthroline complex viaa maleimide linker. [ABSTRACT FROM AUTHOR]