含吡唑雙亞硝基鐵錯合物之合成、結構鑑定與反應性探討

Synthesis, Structural Characterization, and Reactivity Study of Pyrazolate- Containing Dinitrosyl Iron Complexes

李丞育(Cheng-Yu Li)

指導教授 ： 魯才德

中原大學/理學院/化學研究所/碩士(2015年)

https://doi.org/10.6840/cycu201500604

摘要

本研究成功的利用吡唑(pyrazole)做為配位體，合成出一系列的雙亞硝基鐵錯合物{Fe(NO)2}9-{Fe(NO)2}9, {Fe(NO)2}9-{Fe(NO)2}10, {Fe(NO)2}10-{Fe(NO)2}10 [(NO)2Fe(-RPyr)2Fe(NO)2]0/1-/2- (R = Me, Me2)。其中三者的氧化還原交互轉換調整了Fe-Fe間距離(3.333-4.079 Å)以及兩個[FeN2Fe]平面之間的角度(120.0o-180.0o)。
進一步利用去氫的吡唑可使雙核的{Fe(NO)2}9-{Fe(NO)2}9 DNIC [(NO)2Fe(-RPyr)2Fe(NO)2]斷裂鐵氮鍵形成單核的{Fe(NO)2}9 DNIC [(RPyr)2Fe(NO)2]-，而布羅酸(醋酸)與路易士酸(醋酸鋅、三氟化硼)則又能使單核的{Fe(NO)2}9 DNIC [(RPyr)2Fe(NO)2]-脫去一個pyrazolate，轉換回雙核的{Fe(NO)2}9-{Fe(NO)2}9 DNIC [(NO)2Fe(-RPyr)2Fe(NO)2]。
參考過去文獻，將[Fe(NO)2]中心穩定小分子以及受阻式路易士酸鹼對穩定小分子的概念做連結，合成出以雙亞硝基鐵錯合物做為基礎架構的受阻式路易士酸鹼對[(NO)2Fe(-RPyr)2Fe(NO)2]- (3-Me, 3-Me2)及[(NO)2Fe(μ-MePyr)2BPin]- (2-Me-BPin)，並探討其活化小分子(O2, CO2, N2O)的特性。
利用[Fe(NO)2]中心可穩定小分子的特性，成功合成出具有成對雙金屬甲烷化合物(gem-dimetallomethanes)結構的DNIC [Fe2(μ-MePyr)(μ-CH2)(NO)2]- (5-Me-K)，具有相當良好的穩定性，並推測能與[H2Pyr][BF4]反應產生甲烷，以及與苯甲酸甲酯反應中，可於其苯環上達到加成甲基的效果而生成4-甲基苯甲酸甲酯。該化合物針對其他有機化合物在亞甲基化反應的特性仍待進一步的探討。

關鍵字

雙亞硝基鐵錯合物

並列摘要

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.

並列關鍵字

DNIC

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