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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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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2013-08

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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.

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University of Minnesota Ph.D. dissertation. August 2013. Major: Chemistry. Advisors: David Blank, Kristopher McNeill. 1 computer file (PDF); viii, 109 pages.

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Pelton, Emily. (2013). A Mechanistic Investigation Into the Photochemistry of an Iron(0) Complex in C-Cl, C-H, and C-F Bond Activation. Retrieved from the University Digital Conservancy, https://hdl.handle.net/11299/175297.

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