[[alternative]]Synthesis and characterization of Co/Fe dinitrosyl complexes with carbonyl N-Heterocyclic Carbenes(NHCs) and P2S2 ligand coordination environment

碩士[[abstract]]雙亞硝基鐵化合物 (DNICs) 在生物體之主要功能為傳遞與儲存一氧化氮，本論文乃透過置換中心金屬合成類似雙亞硝基鐵化合物的雙亞硝基鈷化合物，並以含氮異環碳烯 N-Heterocyclic Carbenes(NHCs) 為配位基合成一系列亞硝基鈷化合物，使用 [Fe(TPP)Cl] 做為一氧化氮 (NO) 捕捉劑對此測試了解釋放 NO之能力，並透過紅外線光譜儀及 X-ray 單晶繞射儀鑑定亞硝基鈷化合物結構。 化合物 [(NO)Fe(N2S2)Fe(NO)2]+ 化合物 (N2S2=N,N’-bis(2-mercapt-oethyl)-1,4-diazacycloheptane) 在2014被發表，可當作還原質子 (H+) 產生氫氣 (H2) 的電催化劑，本篇論文以 meso-1,3Bis[(mercaptoethyl)phenylphosphino] propane (H2meppp) 做為配位基，目標是能合成出類似結構，且比較P與N做配位時，特性與穩定度的不同以求改良並藉由紅外線光譜探討其配位方式。[[abstract]]The primary functions of Dinitrosyl iron complexes (DNICs) in vivo are transportation and storage of Nitric oxide (NO). In here, we report a series of synthetic analogs of DNICs by using cobalt as metal center and N-Heterocyclic Carbenes (NHCs) as ligands. We measure the NO releasing ability of nitrosyl cobalt complexes by using [Fe(TPP)Cl] as NO trapping agent . Thesenitrosyl cobalt complexes were characterized by Fourier transform infrared spectroscopy (FTIR), UV-vis spectroscopy, Nuclear magnetic resonance (NMR) and Single crystal X-ray Diffraction. The cationic [(NO)Fe(N2S2)Fe(NO)2]+ complexes have been published in 2014 (N2S2 = N,N’-bis(2-mercaptoethyl)-1,4-diazacycloheptane). The cationic dinucleardinitrosyl iron complex was found to be electro catalyst for H+ reduction,in term of H2 production. We report a series of synthetic analogs of [(NO)Fe(N2S2)Fe(NO)2]+/-by using(CO)2Fe(NO)2,(CO)3Co(NO) and meso-1,3Bis[(mercaptoethyl)phenylphosphino] propane (H2meppp) as ligands, andcompare the differences of stability and properties between the P and N atom of the ligand. The coordination and the possible structures are also discussed and characterized by its Fourier transform infrared (FTIR) spectra.[[tableofcontents]]摘要 Abstract 謝誌 第一章緒論.........................................................................................1 1.1 前言..................................................................................................1 1.2一氧化氮的分子特性.......................................................................2 1.3 一氧化氮在生物體內的性質..........................................................3 1.4一氧化氮在生物體內儲存與傳遞...................................................5 1.5雙亞硝基鐵化合物(DNICs) ...........................................................6 1.6氮雜環碳烯(N-Heterocyclic Carbenes，NHCs).........................10 1.7含磷硫配位基.................................................................................12 1.8鈷在生體中的應用.........................................................................13 1.9 研究目標........................................................................................14 第二章結果與討論............................................................................16 2.1鈷化合物(NHC-Me)(CO)2Co(NO) (1)、(NHC-Me)2(CO)Co(NO)(2)與(NHC-Me)2Co(NO)2 (3) 的合成與紅外線光譜分析..............16 2.2鈷化合物(NHC-Me)(CO)2Co(NO) (1) 、(NHC-Me)2(CO)Co(NO) (2) 與 [(NHC-Me)2Co(NO)2][BF4] (3) 的X-ray X光單晶繞射分析...........................................................................................................21 2.3鈷化合物(NHC-Me)(SPh)Co(NO)2 (4) 與 (NHC-Me)(SEt)Co(NO)2 (5) 的合成與紅外線光譜分析..................25 2.4不同配位基之鈷化合物的紅外線光譜、結構的探討.................31 2.5不同配位基之鈷化合物循環伏安法的探討.................................36 2.6亞硝基鈷化合物與[Fe(TPP)Cl]的反應探討...............................40 2.7雙磷雙硫配位基的鐵/鈷金屬化合物的合成與紅外線光譜分析42 第三章結論........................................................................................49 第四章實驗部分................................................................................51 參考文獻............................................................................................63 附錄....................................................................................................66 2.2鈷化合物(NHC-Me)(CO)2Co(NO) (1) 、(NHC-Me)2(CO)Co(NO) (2) 與 [(NHC-Me)2Co(NO)2][BF4] (3) 的X-ray X光單晶繞射分析...........................................................................................................21 2.3鈷化合物(NHC-Me)(SPh)Co(NO)2 (4) 與 (NHC-Me)(SEt)Co(NO)2 (5) 的合成與紅外線光譜分析..................25 2.4不同配位基之鈷化合物的紅外線光譜、結構的探討.................31 2.5不同配位基之鈷化合物循環伏安法的探討.................................36 2.6亞硝基鈷化合物與[Fe(TPP)Cl]的反應探討...............................40 2.7雙磷雙硫配位基的鐵/鈷金屬化合物的合成與紅外線光譜分析42 第三章結論........................................................................................49 第四章實驗部分................................................................................51 參考文獻............................................................................................63 附錄....................................................................................................66 圖目錄 圖1-1 一氧化氮分子軌域圖……………………………………………2 圖1-2 Enemark-Feltham的計算法………………………………………4 圖1-3 半胱氨酸與穀胱甘肽之結構…………………………………6 圖1-4 生理條件下 DNICs 儲存、運輸及傳遞NO 的可能路徑，RS為cysteine或glutathione (GSH)……………………………………….7 圖1-5 生物體中大腸桿菌細胞中的ferredoxin [2Fe2S] cluster 的降解與修復……………………………………………………………………8圖1-6 在仿生研究中三個RRE與DNIC不同轉換的途徑…………..9 圖1-7 含氮異環碳烯(NHCs) 與金屬的反應………………………..10 圖1-8 Ofele合成鉻金屬錯化合物……………………………………..10 圖1-9 (a)鎳鐵氫化酶(b) Tomoaki Tanase以 H2meppp 與過渡金屬合成之結構..................................................................................................13 圖1-10 維生素B12的結構……………………………………………..14 圖2-1 起始物與化合物1在室溫下四氫呋喃的紅外線光譜疊圖…...19 圖2-2 化合物1與化合物2在室溫下四氫呋喃的紅外線光譜疊圖…20 圖2-3 化合物1之晶體結構…………………………………………...22 圖2-4 化合物2之晶體結構…………………………………………...22 圖2-5 化合物3之晶體結構及鍵長[Å]與鍵角[°].............................24 圖2-6 化合物3、化合物4與化合物5在室溫下二氯甲烷的紅外線光譜疊圖…………………………………………………………………..26 圖2-7 (IMes)(HSO4)Co(NO)2 之晶體結構及鍵長[Å]與鍵角[°]........30 圖2-8 (IMes)(SPh)Co(NO)2 之晶體結構及鍵長[Å]與鍵角[°]……...31 圖2-9 化合物b與化合物2在室溫二氯甲烷溶液中的循環伏安圖…37 圖2-10 化合物c與化合物 3在室溫二氯甲烷溶液中的循環伏安圖39 圖2-11 化合物2與[Fe(TPP)Cl]在0℃下的紅外線光譜圖 (CH2Cl2)...40 圖2-12 化合物3與[Fe(TPP)Cl]在0℃下的紅外線光譜圖 (CH2Cl2)..41 圖2-13 起始物Fe(CO)2 (NO)、化合物7在室溫下在THF中的紅外線光譜疊圖………………………………………………………………..43 圖2-14 推測化合物7可能之結構…………………………………….44 圖2-15 起始物 Co(CO)3(NO)、化合物8在室溫下在THF中的紅外線光譜疊圖………………………………………………………………..45 圖2-16 推測化合物8可能之結構…………………………………….45 圖2-17 化合物7、化合物9在室溫下在THF中的紅外線光譜疊圖....46 圖2-18 推測化合物9可能之結構…………………………………….47 圖2-19 化合物8、化合物10在室溫下在THF中的紅外線光譜疊圖..48 圖2-20 推測化合物10可能之結構…………………………………...48 圖2-5 化合物3之晶體結構及鍵長[Å]與鍵角[°].............................24 圖2-6 化合物3、化合物4與化合物5在室溫下二氯甲烷的紅外線光譜疊圖…………………………………………………………………..26 圖2-7 (IMes)(HSO4)Co(NO)2 之晶體結構及鍵長[Å]與鍵角[°]........30 圖2-8 (IMes)(SPh)Co(NO)2 之晶體結構及鍵長[Å]與鍵角[°]……...31 圖2-9 化合物b與化合物2在室溫二氯甲烷溶液中的循環伏安圖…37 圖2-10 化合物c與化合物 3在室溫二氯甲烷溶液中的循環伏安圖39 圖2-11 化合物2與[Fe(TPP)Cl]在0℃下的紅外線光譜圖 (CH2Cl2)...40 圖2-12 化合物3與[Fe(TPP)Cl]在0℃下的紅外線光譜圖 (CH2Cl2)..41 圖2-13 起始物Fe(CO)2 (NO)、化合物7在室溫下在THF中的紅外線光譜疊圖………………………………………………………………..43 圖2-14 推測化合物7可能之結構…………………………………….44 圖2-15 起始物 Co(CO)3(NO)、化合物8在室溫下在THF中的紅外線光譜疊圖………………………………………………………………..45 圖2-16 推測化合物8可能之結構…………………………………….45 圖2-17 化合物7、化合物9在室溫下在THF中的紅外線光譜疊圖....46 圖2-18 推測化合物9可能之結構…………………………………….47 圖2-19 化合物8、化合物10在室溫下在THF中的紅外線光譜疊圖..48 圖2-20 推測化合物10可能之結構…………………………………...48 附錄 圖S1化合物1溶於THF的紅外線光譜圖…………………………….66 圖S2化合物2溶於THF的紅外線光譜圖……………………………66 圖S3化合物3溶於CH2Cl2的紅外線光譜圖…………………………67 圖S4化合物4溶於CH2Cl2的紅外線光譜圖…………………………67 圖S5化合物5溶於CH2Cl2的紅外線光譜圖…………………………68 圖S6化合物6溶於CH2Cl2的紅外線光譜圖…………………………68 圖S7化合物7溶於THF的紅外線光譜圖…………………………….69 圖S8化合物8溶於THF的紅外線光譜圖…………………………….69 圖S9化合物9溶於THF的紅外線光譜圖…………………………….70 圖S10化合物10溶於Toluene的紅外線光譜圖………………………70 圖S11(H2meppp)溶於CDCl3的31P NMR光譜…………………….…71 圖S12化合物3溶於CH2Cl2的紫外/可見光光譜圖…………………72 圖S13化合物6溶於CH2Cl2的紫外/可見光光譜圖…………………72 Table S1 Crystal data and structure refinement for 2………………..73 Table S2 Bond lengths [Å] and angles [°] for 2……………………..75 Table S3 Crystal data and structure refinement for 3………………..76 Table S4 Bond lengths [Å] and angles [°] for 3……………………..77 Table S5 Crystal data and structure refinement for 6………………..78 Table S6 Bond lengths [Å] and angles [°] for 6……………………..79 Table S7 Crystal data and structure refinement for (IMes)(HSO4)Co(NO)2…………………………...……………………..82 Table S8 Bond lengths [Å] and angles [°] for (IMes)(HSO4)Co(NO)2 …….………………………..…………………………...………………84[[note]]學號: 604160381, 學年度: 10

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