含硼氫化物之雙亞硝基鐵錯合物合成、結構與反應性探討

本篇研究利用{Fe(NO)2}10 單核DNICs [(NO)2Fe(TMEDA)]，與硼氫化物(BH4-)進行置換反應，成功合成出帶有負電荷單核{Fe(NO)2}10DNICs [(NO)2Fe(η2-BH4)]- (1)，並且利用XRD, IR, NMR輔助判斷鐵與硼之間以兩個氫作為橋接，探討其晶體結構。除此之外亦成功合成出單{Fe(NO)2}10 DNICs[(NO)2(CO)Fe(NCBH3)]-(3) 並且探討與化合物 1 或是化合物[(NO)2Fe(TMEDA)]之間的相互轉換。參考過去文獻金屬硼氫化物和路易士酸鹼對活化小分子的概念，我們嘗試利用化合物 1 與CO2進行反應性的探討，反應後主結構[Fe(NO)2]會瓦解，伴隨著BH4-將CO2活化生成[HB(OCHO)3] -, [H2B(OCHO)2] -。並利用結構相似反應性更¬好的CS2進行反應，成功合成出單核{Fe(NO)2}10 DNICs[(NO)2Fe(η3--(S,C,S)-SCHS)]-(2)由XRD；NMR，得知中心鐵是以η3的建結模式與Dithioformate(HCS2)形成鍵結，比照過去文獻為鮮少的例子。由化合物1與CS2反應得知，化合物 1與CO2反應時需要配位基來幫助穩定{Fe(NO)2}的主結構，利用TMEDA螯合取代基和化合物 1在CO2環境下反應後成功的合成出化合物[(NO)2Fe(TMEDA)]，並且達到一循環反應。

關鍵字

雙亞硝基鐵錯合物；過度金屬硼氫化物；二氧化碳；二硫化碳

並列摘要

In this work, using borohydride (BH4-) produce ligand exchange with mononuclear DNICs [(NO)2Fe(TMEDA)],and we successfully synthesis mononuclear dinitrosyl iron complex(DNIC) containing borohydride {Fe(NO)2}10[(NO)2Fe- (η2-BH4)]- (1). Complex 1 contains two hydride bridging iron and boron atoms, which was charcterized by XRD, IR, NMR, and discussed the crystal structure. In addition to that we successfully synthesized mononuclear Dinitrosyl iron complex (DNIC) containing cyanoborohydride {Fe(NO)2}10[(NO)2(CO)Fe(NCBH3)]- (3), which will be discussed the relationship with complex 1 or complex [(NO)2Fe(TMEDA)]. Inspired by the concept ion of small molecules activated by the transition metal borohydride complex and the frustrated lewis pairs (FLPs). Complex 1 reacts with CO2 making the structure of [Fe(NO)2] decoposed and concomitant produce [HB(OCHO)3] –,[H2B(OCHO)2] -. However, we attempted to react with CS2 ,which was more active than CO2, and succefully synthesized mononuclear dinitrosyl iron complex (DNIC) {Fe(NO)2}10[(NO)2 Fe(η3¬-(S,C,S)-SCHS)] (2), was charcterized by XRD, IR and NMR . It is a rare example for transition metal binding dithioformate (HCS2) as η3 mode. According to this reaction knows that complex 1 react with CO2 need ligand to stabilize the structure of [Fe(NO)2]. We succefully used TMEDA ligand to stablize structure of [Fe(NO)2] and succefully synthesis complex [(NO)2Fe(TMEDA)]. This is important point to achieve cycle reaction.

並列關鍵字

dinitrosyl iron complex(DNIC) ； transition metal tetrahydroborate complexes ； carbon dioxide ； carbon disulfide

參考文獻

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含硼氫化物之雙亞硝基鐵錯合物合成、結構與反應性探討

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