The continuously increasing concentration of the greenhouse gas carbon dioxide (CO2) in Earth’s atmosphere combined with its inexpensive cost has made CO2 upconversion an area of intense interest in catalysis research. One of the most challenging reactions of CO2 to date has been the reductive coupling of CO2 with other small molecules to produce C-C bonds. This presentation describes the synthesis and reactivity of a new series of low valent iron complexes based on triphosphine ligands, tBuP(CH2CH2PR2)2 (R = Et, iPr, Cy). The coordination chemistry of the complexes in solid-state and in solution has been characterized, and the reactivity of the complexes toward reductive CO2 functionalization has been explored. Several complexes have proven active for CO2 reduction, including the formation of new C-C bonds derived from CO2. Structure-reactivity relationship studies reveal significant differences in reactivity for complexes bearing related alkyl phosphine donor ligands.

Synthesis and reactivity of novel low valent iron for reductive functionalization of carbon dioxide

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