| Summary: | 碩士 === 中原大學 === 化學研究所 === 103 === In this work, dinuclear DNICs containing pyrazolate bridging ligands [(NO)2Fe(-RPyr)2Fe(NO)2]0/1-/2- (Pyr = pyrazolate, R = H, Me, Me2) were successfully synthesized. Redox interconversion among {Fe(NO)2}9-{Fe(NO)2}9, {Fe(NO)2}9-{Fe(NO)2}10, {Fe(NO)2}10-{Fe(NO)2}10 dinuclear DNICs regulates the Fe…Fe distance between 3.333-4.079 Å and the angles between two [FeN2Fe] planes 120.0o-180.0o.
Reaction of deprotonated pyrazolate with dinuclear DNIC{Fe(NO)2}9-{Fe(NO)2}9 [(NO)2Fe(-RPyr)2Fe(NO)2] generates mononuclear DNIC {Fe(NO)2}9 [(RPyr)2Fe(NO)2]-1. This complex will convert into dinuclear DNIC{Fe(NO)2}9-{Fe(NO)2}9 [(NO)2Fe(-RPyr)2Fe(NO)2] by reacted with Brønsted–Lowry acid and Lewis acids.
Inspired by the characterization of small molecules stablized by [Fe(NO)2] centers.To combine the concept of small molecules stablized and activated by the frustrated lewis pair (FLP), the FLP-like DNICs [(NO)2Fe(-RPyr)2Fe(NO)2]1- (3-R, R = Me, Me2) and [(NO)2Fe(μ-MePyr)2BPin]1- (2-Me-BPin) were successfully synthesized.The reactivity of these DNICs with O2, CO2, N2O were studied in this work.
Compounds with two metal atoms on the same carbon of CH2, categorized as gem-dimetallomethanes (H2CM1M2), constitute a classic and important class of organometallic reagents in organic synthesis. Because of the characterization of small molecules stablized by [Fe(NO)2] centers, the DNIC [Fe2(μ-MePyr)(μ-CH2)(NO)2]- (5-Me-K) with two [Fe(NO)2] centers binding on the same carbon of CH2 was successfully synthesized in this work.This DNIC is much more stable than other reported gem-dimetallomethanes compounds.Formation of Methane in the reaction of 5-Me-K and [H2Pyr][BF4] was been conjectured.The reactivity of methyl addition was insighted by the reaction of 5-Me-K and Methyl benzoate.
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