含N配位之雙亞硝基鐵化合物的合成、反應性以及對酚類硝化反應性探討

本研究合成{Fe(NO)2}10 [Fe(NO)2(PMA)] (1)、{Fe(NO)2}10 [Fe(NO)2(PMDTA)] (2)、{Fe(NO)2}10 [Fe(NO)2(DPA)] (3)、{Fe(NO)2}10 [Fe(NO)2(4-pry)] (4)、{Fe(NO)2}9 [Fe(NO)2(PMDTA)][BF4] (5)、{Fe(NO)2}9 [Fe(NO)2(DPA)][PF6] (6)、{Fe(NO)2}9 [Fe(NO)2(4-pry)][BF4] (7)、{Fe(NO)2}10-{Fe(NO)2}10 [Fe2(NO)4(TPEN)] (8)、{Fe(NO)2}9-{Fe(NO)2}9 [Fe2(NO)4(TPEN)][BF4]2 (9)、{Fe(NO)2}9 [Fe(NO)2(TPEN)][BF4] (10)，並且以IR,UV-vis, CV, XAS, EPR,X-ray單晶繞射鑑定。由反應性探討中得知complex 3, 6、complex 4, 7與complex 8, 9彼此分別可利用氧化還原反應互相轉換，且利用CV進一步證實；而藉由EPR、NMR可以得知complex 1, 3, 4為順磁性化合物而complex 5, 6, 7, 9, 10為逆磁性化合物。另外，將化合物1, 3, 4, 5, 6, 7, 10與2,4-di-tert-butylphenol在氧氣存在的條件下反應，並利用GC-MS偵測2,4-di-tert-butylphenol被硝化後生成2,4-di-tert-butyl-6-nitrophenol的產率，藉此探討不同配位基與電子結構化合物在氧氣條件下對於2,4-di-tert-butylphenol硝化能力的差異。希望能藉由本研究進一步了解以N做為配位基形式的{Fe(NO)2}10以及{Fe(NO)2}9 DNICs，在生物系統中扮演的角色與可能的反應路徑。

關鍵字

一氧化氮；雙亞硝基鐵化合物；氧氣；酚類硝化

並列摘要

{Fe(NO)2}10 [Fe(NO)2(PMA)] (1), {Fe(NO)2}10 [Fe(NO)2(PMDTA)] (2), {Fe(NO)2}10 [Fe(NO)2(DPA)] (3), {Fe(NO)2}10 [Fe(NO)2(4-pry)] (4), {Fe(NO)2}9 [Fe(NO)2(PMDTA)][BF4] (5), {Fe(NO)2}9 [Fe(NO)2(DPA)][PF6] (6), {Fe(NO)2}9 [Fe(NO)2(4-pry)][BF4] (7), {Fe(NO)2}10-{Fe(NO)2}10 [Fe2(NO)4(TPEN)] (8), {Fe(NO)2}9-{Fe(NO)2}9 [Fe2(NO)4(TPEN)][BF4]2 (9) and {Fe(NO)2}9 [Fe(NO)2(TPEN)][BF4] (10) were synthesized and characterized by IR, UV-vis, CV, XAS, EPR, and single-crystal X-ray diffraction. The reversible interconversion between complexe 3 and 6 / 4 and 7 / 8 and 9 was also demonstrated and consistent with cyclic voltammograms. In addition, to study the phenol nitrating ability of DNICs with different coordination environment and electronic structures, the complex 1, 3, 4, 5, 6, 7 and 10 were reacted with 2,4-di-tert-butylphenol in the presence of O2, and the yield of phenol nitration product - 2,4-di-tert-butyl-6-nitrophenol was dected by GS-MS.