Photocatalysts offer an effective way to initiate chemical reactions that are reductive or oxidative in nature. The use of Earth-abundant first-row transition-metal ions such as V, Cr, Ni, Cu to photochemically activate C=O and C=N π bonds is desirable, especially in the context of replacing expensive 1-electron reagents for organic synthesis, such as SmI<sub>2</sub>. Employing Schiff-base ligands with four nitrogen donor atoms, we have made complexes that absorb strongly in the visible spectrum and have open metal coordination sites for binding substrates. The complex Ni(thb) (thb = ((13E, 19E)-5,6,7,8-tetrahydrotribenzo[<i>b,f,l</i>][1,4,8]tetraazacyclotetradecine) has proven to be a strong absorber and capable of binding both benzaldehyde and acetylaldehyde. The synthesis, characterization, and catalytic screening of [Ni(thb)] and other metal analogs will be discussed.

Toward inner-sphere photoactivation of carbonyl and imine groups using Earth-abundant Schiff-base photocatalysts

249th National Meeting (2015)

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