由高自旋非血基質亞鐵硝酰基錯合物與酸反應生成具HNO之鐵錯合物

Abstract

本研究利用三氮二氧五牙基H2(BDPBrP)與鐵二價金屬離子反應形成前驅物FeII(BDPBrP) (1)。將一氧化氮氣體通入前驅物1會形成亞鐵硝酰基錯合物Fe(BDPBrP)(NO) (2)，再加入三氟磺酸會生成Fe(BDPBrP)(HNO) (4)，為了確認反應生成錯合物4，加入一當量的強鹼試劑DBU，去質子化生成錯合物2，藉由紫外-可見光光譜(UVvis)、低溫即時紅外光譜(low temperature in-situ IR)以及電子順磁共振光譜（Electron Paramagnetic Resonance，EPR）證明錯合物2及錯合物4的存在。 利用三苯基磷與錯合物4反應形成PPH3=O和PPH3=NH， 再藉由電噴灑離子化質譜(ESI-Mass)去鑑定PPH3=O和PPH3=NH的存在，來證明Fe(BDPBrP)(HNO) (4)的生成。

In this study, N3O2 petadentate ligand H2(BDPBrP), was reacted with FeCl2 to form FeII(BDPBrP) (1) precursor, which can further react with nitric oxide to produce ferrous nitroxyl complex Fe(BDPBrP)(NO) (2) complex. Addition of triflic acid to complex 2 resulted in the formation Fe(BDPBrP)(HNO) (4). To further confirm the identity of complex 4 , one equiv of strong base (DBU) was reacted with the complex 4. After deprotonation, 2 was regenerated. UVvis , low temperature in-situ IR and Electron Paramagnetic Resonance spectroscopies were performed to determined complex 2 and 4. PPH3=O and PPH3=NH was produced and characterized by ESI-Mass from the reacting mixture of Triphenylphosphine with 4 in THF, Indicates the presence of HNO containing complex 4.