以三氮二氧配位基形成過氧亞硝酸鈷錯合物之鑑定

Formation and Identification of Cobalt Peroxynitrite Supported by N3O2 Ligands

葉凱鈞(Yeh Kai-Chun)

指導教授 ： 李位仁

國立臺灣師範大學/理學院/化學系/碩士(2017年)

https://doi.org/10.6345/NTNU202202937

摘要

["本次研究利用H2BDPP及衍生物H2BDPBrP兩種N3O2配位基與鈷金屬離子反應形成CoIIBDPP (1)和CoIIBDPBrP (1')起始物。它們個別與氧氣反應會先形成CoIIIBDPP(O2) (2)及CoIIIBDPBrP(O2) (2')，再與一氧化氮反應會得到過氧亞硝酸三價鈷錯合物CoIIIBDPP(OONO) (3) 和CoIIIBDPBrP(OONO) (3') 。藉由紫外-可見光光譜(UV-vis)以及低溫即時紅外光譜(low temperature in-situ IR)說明錯合物3'的存在，錯合物3'會轉變成三價鈷與水鍵結的錯合物，可以四氫呋喃/乙醚擴散法得到[CoIIIBDPBrP(H2O)]NO3 (4')晶體，錯合物4'的硝酸根陰離子以15N標定其氮原子，並且利用電噴灑離子化質譜(ESI-Mass)、低溫核磁共振光譜(NMR)以及紅外光譜受到同位素影響產生震動位移證明這個產物。"]

關鍵字

過氧亞硝酸 ； 鈷錯合物

並列摘要

["In this study, N3O2 petadentate ligands H2BDPP and H2BDPBrP react with CoCl2 to form cobalt precursors, CoIIBDPP (1) and CoIIBDPBrP (1'). By reacting with O2, Complexes 1 and 1' were employed to generate CoIIIBDPP(O2) (2) and CoIIIBDPBrP(O2) (2'), which then react with NO to produce Co(III)-peroxynitrite complex, CoIIIBDPP(OONO) (3) and CoIIIBDPBrP(OONO) (3'). UV-vis and low temperature in-situ IR spectroscopies were performed to determined complex 3', which was converted into an aqua-bonded cobalt(III) complex, [CoIIIBDPBrP(H2O)]NO3 (4'), crystallized by THF/ether diffusion. The nitrate anions of 4' was characterized by 15N-labbelled ESI-MS and IR spectroscopy showing corresponding isotope shift. The formation of nitrate in 4' is suggested via a rearrangement of the peroxynitrite ligand."]

並列關鍵字

none

參考文獻

英文文獻

1.PA´ L PACHER, JOSEPH S. BECKMAN, and LUCAS LIAUDET, Physiol Rev, 2007, 87, 315–424

2.Leila Mahmoudi, Reinhard Kissner, and Willem H. Koppenol, Inorg. Chem. 2017, 56, 4846−4851

3.Mark P. Schopfer, Jun Wang, and Kenneth D. Karlin, Inorg. Chem. 2010, 49, 6267–6282

4.Nhut Giuc Tran, Harris Kalyvas, Kelsey M. Skodje, Takahiro Hayashi, Pierre Mo€enne-Loccoz, Paige E. Callan, Jason Shearer, Louis J. Kirschenbaum,