Expanding the PCET Thermochemistry of Cp^N3: N-H Bond Strengths of Metal-Free Cp^N3 Molecules and the Influence of Fe(CO)₃ Coordination.

ABSTRACT: Amine rich cyclopentadienyl (Cp^N3) ligands are electronically distinct from classical Cp ligand architectures, as they exhibit fascinating proton-coupled electron transfer (PCET) chemistry under acidic conditions in the presence and absence of transition metals. We now report that the exocyclic N-H bond of the isopropylamine moiety in [^RCp^N3]⁺ can be deprotonated under basic conditions (R = ⁱPr, ^t Bu), enabling the experimental determination of N-H bond strengths via pK _a and redox potential measurements in acetonitrile. From these data, the experimentally determined N-H acidity and bond dissociation free energy of [^iPrCp^N3]⁺ are pK _a = 22.6 and BDFE

SUBMITTER: Tresp DS 

PROVIDER: S-EPMC12492044 | biostudies-literature | 2025 Oct

REPOSITORIES: biostudies-literature