Photoinitiated Reactivity of a Thiolate-Ligated, Spin-Crossover Nonheme {FeNO}(7) Complex with Dioxygen.

ABSTRACT: The nonheme iron complex, [Fe(NO)(N3PyS)]BF4, is a rare example of an {FeNO}(7) species that exhibits spin-crossover behavior. The comparison of X-ray crystallographic studies at low and high temperatures and variable-temperature magnetic susceptibility measurements show that a low-spin S = 1/2 ground state is populated at 0-150 K, while both low-spin S = 1/2 and high-spin S = 3/2 states are populated at T > 150 K. These results explain the observation of two N-O vibrational modes at 1737 and 1649 cm(-1) in CD3CN for [Fe(NO)(N3PyS)]BF4 at room temperature. This {FeNO}(7) complex reacts with dioxygen upon photoirradiation with visible light in acetonitrile to generate a thiolate-ligated, nonheme iron(III)-nitro complex, [Fe(III)(NO2)(N3PyS)](+), which was characterized by EPR, FTIR, UV-vis,

SUBMITTER: McQuilken AC 

PROVIDER: S-EPMC5502531 | biostudies-literature | 2016 Mar

REPOSITORIES: biostudies-literature