Application of the Marcus cross relation(MCR)to determine electron transfer rate constants is well documented.In addition to outer sphere reduction/oxidation of O_(2)/O_(2)^(·−),the MCR is also applicable for pro...Application of the Marcus cross relation(MCR)to determine electron transfer rate constants is well documented.In addition to outer sphere reduction/oxidation of O_(2)/O_(2)^(·−),the MCR is also applicable for proton transfer(PT),proton-coupled electron transfer(PCET),and hydride transfer rate constants.A question this report aims to address is whether or not the MCR can predict rate constants for inner sphere electron transfer(ISET)reactions between iron complexes and O_(2).By including the iron–superoxide bond dissociation energy(BDFEFe–O_(2))into the MCR equilibrium constant,close values to experimental inner sphere O_(2) reductions are estimated.This insight of including the iron–superoxide binding energy as a design element for the development of synthetic oxygenases is considered.展开更多
文摘Application of the Marcus cross relation(MCR)to determine electron transfer rate constants is well documented.In addition to outer sphere reduction/oxidation of O_(2)/O_(2)^(·−),the MCR is also applicable for proton transfer(PT),proton-coupled electron transfer(PCET),and hydride transfer rate constants.A question this report aims to address is whether or not the MCR can predict rate constants for inner sphere electron transfer(ISET)reactions between iron complexes and O_(2).By including the iron–superoxide bond dissociation energy(BDFEFe–O_(2))into the MCR equilibrium constant,close values to experimental inner sphere O_(2) reductions are estimated.This insight of including the iron–superoxide binding energy as a design element for the development of synthetic oxygenases is considered.
