Through mechanistic work and rational design, we have developed the fastest abiotic Cys bioconjugation. As a result, the developed organometallic Au(III) bioconjugation reagents enable selective labelling of Cys moieties down to pM concentrations and allow for the rapid construction of complex heterostructures from peptides, proteins, and oligonucleotides. This work showcases how organometallic chemistry can be interfaced with biomolecules and lead to the range of reactivities that are unmatched by classical organic chemistry tools.
A nickel bromide complex supported by a non-innocent ferrocene-chelating heteroscorpionate ligand, [(fc(PPh2)(BH(3,5-Me2pz)2)NiBr] ((fcP,B)NiBr, fc = 1,1’-ferrocenediyl, pz = pyrazole), was synthesized and characterized. The compound can be readily oxidized according to UV-vis and 1H NMR spectroscopy. The catalytic activity of the compound’s different oxidation states in the polymerization of vinyl monomers was explored. AB and ABA-type block copolymers were made from styrene and p-chlorostyrene, offering an example of orthogonal redox control in radical polymerization.
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