雙亞硝基鈷化合物包含磷及硫的合成、性質與X-ray單晶結構鑑定

Phosphine/Thiolate Containing Dinitrosyl Cobalt Complexes (DNCCs): Synthesis, Characterization and X-ray Diffraction Identification

張文劼(Wei-Chieh Chang)

指導教授 ： 謝忠宏

淡江大學/理學院/化學學系碩士班/碩士(2016年)

https://doi.org/10.6846/TKU.2016.00855

摘要

Dinitrosyl iron complexes (DNICs)近年來被廣泛的研究，它在生物體內儲存及傳遞一氧化氮的功能備受重視，為了解一氧化氮在不同金屬中的配位性及釋放能力，我們以鈷為金屬中心合成了一系列類似DNICs的化合物，並用[Fe(TPP)Cl]當作NO捕捉劑測試{Co(NO)}10和{Co(NO)2}10化合物的一氧化氮釋放能力，亞硝基鈷化合物的電子數我們利用Enemark-Feltham提出的{M(NO)x}n方法計算。鈷化合物的合成以(CO)3Co(NO)作為起始物，分別加入一、二倍的PPh3形成neutral {Co(NO)}10 (PPh3)(CO)2Co(NO) (1)和{Co(NO)2}10 (PPh3)2(CO)Co(NO) (2)，化合物2可以與NOBF4反應產生cationic {Co(NO)2}10 [(PPh3)2Co(NO)2][BF4] (3)，而化合物3能加入一或二倍的NaSPh形成neutral {Co(NO)2}10 (PPh3)(SPh)Co(NO)2 (4)和anionic {Co(NO)2}10 [(SPh)2Co(NO)2][PPh4] (5)，最後化合物5我們利用HBF4進行質子化產生三聚體的{Co(NO)2}10 [Co3(NO)6(μ-SPh)3] (6)。亞硝基鈷化合物的鑑定主要是藉由紅外線光譜儀及X-ray單晶繞射儀進行。

關鍵字

DNICs ； RRE ； 一氧化氮 ； NO trapping agent

並列摘要

Dinitrosyl iron complexes (DNICs) are organometallic-like compounds of biological significance in that they appear in vivo; synthetic analogues have potential as NO storage and releasing agents. In here we report the synthetic analogs of DNICs by using cobalt as a metal center. The (CO)3Co(NO) was adopted as a starting material and reacted with PPh3 to yield the neutral {Co(NO)}10 complex (PPh3)(CO)2Co(NO) (1). Complex 1 was further reacted with NOBF4 and PPh3 to yield the cationic {Co(NO)2}10 complex [(PPh3)2Co(NO)2][BF4] (3). The respectively NaSPh was added to replace one PPh3 to form a neutral mixed ligand {Co(NO)2}10 complex (PPh3)(SPh)Co(NO)2 (4). Reaction of complex 4 with additional one equivalent of [PPh4][SPh] to produce the anionic {Co(NO)2}10 complex [(SPh) 2Co(NO)2][PPh4] (5). We used [Fe(TPP)Cl] as NO trapping agent to measure the NO tranfer ability of nitrosyl cobalt complexes. The cationic, neutral, and anionic {Co(NO)2}10 dinitrosyl cobalt complexes (DNCCs) were synthesized and characterized by Fourier transform infrared (FTIR), UV−vis, Nuclear magnetic resonance (NMR), and X-ray diffraction.

並列關鍵字

DNICs ； RRE ； Nitric oxide ； NO trapping agent

參考文獻

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6. Santolini, J. J. Inorg Biochem 2011, 105, 127-141.

7. Daff, S. Nitric Oxide 2010, 23, 1-11.