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Full-Text Articles in Physical Sciences and Mathematics
Structure And Reactivity Of The First Row Transition Metals Bearing Redox-Active Ligands And Tunable H-Bonding Interactions, Khashayar Rajabimoghadam
Structure And Reactivity Of The First Row Transition Metals Bearing Redox-Active Ligands And Tunable H-Bonding Interactions, Khashayar Rajabimoghadam
Chemistry Theses and Dissertations
Metalloenzymes, as natural catalysts, can break a reaction with high activation energy to multiple small reactions with lower activation energies; in these small reactions, multiple bonds form and dissociate rapidly, some metalloenzymes use redox-active ligands in their active site to provide the needed electrons for these multiple small reactions. Additionally, in the secondary coordination sphere in the vicinity of the metalloenzymes, the hydrogen bonding interactions facilitate the transfer and interaction of the substrates and the stabilization of the active intermediates. These unique features in metalloenzymes inspired chemists to design molecular models that can partially mimic the structure and reactivity of …
Cu-Promoted C-H Bond Hydroxylation Inspired By Cu-Dependent Metalloenzymes, Rachel Trammell
Cu-Promoted C-H Bond Hydroxylation Inspired By Cu-Dependent Metalloenzymes, Rachel Trammell
Chemistry Theses and Dissertations
From 2003 to 2015, Schӧnecker and Baran proposed a dinuclear Cu/O2 species in their mechanistic proposal for the hydroxylation of sp3 C-H bonds within their systems (proposed based on yields). Inspired from the site selectivity of this methodology and poor analysis of the mechanism, the first project was inspired to re-examine the sp3 C-H bond hydroxylation by Schrӧnecker and Baran and perform an intensive investigation into understanding how Cu/O2 interact which led us to propose a new mechanism based on the evidence collected (i.e., LCuII-hydroperoxide species that undergoes homolytic O-O bond cleavage). From there …