The photochemical generation of an Fe(0) model complex and its subsequent reactivity with C-Cl and C-F bonds was investigated in this work. The photochemical generation and ultrafast dynamics of the Fe(0) model complex was studied. The rate of H<sub>2</sub> escape in solvents of various viscosities, as well as the effect of H<sub>2</sub> versus D<sub>2</sub> release, was also investigated, as was the yield of geminate recombination of the Fe(0) complex and H<sub>2</sub> within the solvent cage. The photochemically generated Fe(0) species was then studied for its ability to dechlorinate CE substrates. A mechanistic investigation was conducted, and a hydrogenolysis pathway was observed. Additionally, increased chlorination of the CE substrates was observed to lead to faster rates of dechlorination by the Fe(0) system. C-F activation of fluorobenzene substrates by the parent Fe(II) complex was evaluated, and activation of the C-F bond was proposed to occur via electron transfer within the solvent cage. Competitive C-H activation of nonperfluorinated substrates was observed when light was introduced into the system, similar to the oxidative addition mechanism mediated by the previously investigated Fe(0) species.
University of Minnesota Ph.D. dissertation. August 2013. Major: Chemistry. Advisors: David Blank, Kristopher McNeill. 1 computer file (PDF); viii, 109 pages.
A Mechanistic Investigation Into the Photochemistry of an Iron(0) Complex in C-Cl, C-H, and C-F Bond Activation.
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