以三氮二氧配位基形成過氧亞硝酸鈷錯合物之鑑定

Abstract

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。

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.