| Summary: | 碩士 === 國立清華大學 === 化學系 === 101 === Several chelate-dithiolate-bound DNICs with different backbone length were synthesized. According to single-crystal X-ray structures, reactivity, and cyclic voltammograms, these chelate-dithiolate-bound DNICs show different properties. From the electrochemistry, the {Fe(NO)2}10 DNIC [PPN]2[(NO)2Fe(SC2H4S)] bearing a shorter backbone displays a rather positive midpoint potential compared to [PPN]2[(κ2-S2-o-xylene)Fe(NO)2 bearing a longer backbone. The interaction of [K⋯S] is an important factor to stabilize the {Fe(NO)2}10 DNIC [K(K-18-crown-6-ether)][(κ2-S2-o-xylene)Fe(NO)2]. However, [(NO)2Fe(SC2H4S)]2- was stable with [PPN]+ salt. The oxidation of [PPN]2[(NO)2Fe(SC2H4S)] might occur on S atom, and form a {Fe(NO)2}10-{Fe(NO)}7 product [PPN]2[(NO)2Fe(μ-κ-SC2H4S)2Fe(NO)]. These results infer that the backbone length and bite angle of chelate-dithiolate-bound DNIC could not only modulate the electronic structure of {Fe(NO)2} core, but also influence its stability and reactivity.
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