三氮二氧配位基鈷錯合物之合成、鑑定與 一氧化氮反應性之研究

Abstract

本研究使用本實驗室先前所開發之N3O2 五牙基H2BDPP 和 H2BDPOMeP，經去質子化後與CoCl2 反應生成五配位二價鈷錯合物 Co(BDPP) (1) 及Co(BDPOMeP) (2)，並可將其氧化至三價鈷錯合 物[Co(BDPP)(H2O)](BF4) (3) 與 [Co(BDPOMeP)(H2O)](BF4) (4)。錯 合物1 - 4 使用 X-ray 單晶繞射儀解析其結構，並以紫外－可見光光 譜儀、循環伏安儀等鑑定其物性和化性。在室溫下將錯合物 1 溶入 二氯甲烷，並與一氧化氮反應，從紫外－可見光光譜儀偵測反應溶液 可發現特徵吸收峰出現在380 和525 nm，並在其遠紅外光光譜觀察 到 1615 cm−1 的震動吸收峰，可能生成Co(BDPP)(NO) (5)，在氮氣 下可長時間穩定存在，最後以理論計算加以輔佐其生成的可能性。另 一方面，在室溫下將錯合物 2 溶入二氯甲烷，並與一氧化氮反應， 亦可從紫外－可見光光譜儀偵測到特徵吸收峰在380 及518 nm。有 趣的是此時遠紅外光光譜觀察到1720 cm−1 的震動吸收峰，可能有 Co(BDPOMeP)(NO) (6) 的生成。In this study, N3O2 pentadentate ligands H2BDPP and H2BDPOMeP, previously designed and developed by our lab, were deprotonated and employed to react with CoCl2 to form CoII complexes, Co(BDPP) (1) and Co(BDPOMeP) (2). Complexes 1 and 2 could be oxidized to form CoIII complexes, [Co(BDPP)(H2O)](BF4) (3) and [Co(BDPOMeP)(H2O)](BF4) (4). Complexes 1 - 4 were characterized by X-ray crystallography, UV-vis spectroscopy and cyclic voltammetry. Reaction of complex 1 with NO in CH2Cl2 was detected by UV-vis spectroscopy at room temperature. The absorptions at 380 and 525 nm were observed in the spectrum. Moreover, the reaction solution exhibited a vibrational stretch at 1615 cm-1 in the IR spectrum, suggesting the formation of Co(BDPP)(NO) (5) which was stable under N2(g) and suggested by the DFT calculation. On the other hand, reaction of complex 2 with NO in CH2Cl2 at room temperature was also detected by UV-vis spectroscopy, exhibiting the characteristic absorptions at 380 and 518 nm. Interestingly, the reaction solution exhibited a signal at 1720 cm-1 in its IR spectrum, suggesting the formation of Co(BDPOMeP)(NO) (6).