Preparation of Labile Ni⁺(cyclam) Cations in the Gas Phase Using Electron-Transfer Reduction through Ion-Ion Recombination in an Ion Trap and Structural Characterization with Vibrational Spectroscopy.

ABSTRACT: Gas-phase ion chemistry methods that capture and characterize the degree of activation of small molecules in the active sites of homogeneous catalysts form a powerful new tool to unravel how ligand environments affect reactivity. A key roadblock in this development, however, is the ability to generate the fragile metal oxidation states that are essential for catalytic activity. Here we demonstrate the preparation of the key Ni(I) center in the widely used cyclam scaffold using ion-ion recombination as a gas-phase alternative to electrochemical reduction. The singly charged Ni⁺(cyclam) coordination complex is generated by electron transfer from fluoranthene and azobenzene anions to doubly charged Ni²⁺(cyclam), using the electron-transfer dissociation protocol in a commercial quadrupole ion trap instrument and in a custom-built octopole RF ion trap. The successful preparation of the Ni⁺(cyclam) cation is verified through analysis of its vibrational spectrum obtained using the infrared free electron laser FELIX.

SUBMITTER: Munshi MU 

PROVIDER: S-EPMC5677246 | biostudies-literature | 2017 Oct

REPOSITORIES: biostudies-literature