Spectral annd Electrochemical Characterization of Ruthenium Porphyrins

• Main Authors: Chin-Yu, Chen, 陳青諭
• Other Authors: Su, Y. O.
• Format: Others
• Language: zh-TW
• Published: 1999
• Online Access: http://ndltd.ncl.edu.tw/handle/41703425852288483990

碩士 === 國立臺灣大學 === 化學研究所 === 87 === Three kinds of ruthenium porphyrins Ru(CO)(P) (where P = tetramesitylphenylporphyrin, tetra(2,6-dichlorophenyl)porphyrin and tetrapentafluorophenylporphyrin) have been synthesized. Electrochemical properties of these porphyrins have been studied in different solvents. Spectroelectrochemical measurement of the reduction/oxidation product indicates that the reaction occurs at the porphyin ring. Oxidation of carbonyl-ruthenium tetramesitylphenyl porphyrin (Ru(CO)(TMP)) by mCPBA (meta-chloro-perbenzoic acid) produces dioxo-ruthenium porphyrin (Ru(O)2TMP), which is reversibly oxidize at +1.24 V. Ru(O)2TMP is very sensitive to acids and yields a new species similar to Ru(IV) porphyrin. Thin-layer absorption spectra for oxidation of Ru(O)2TMP at +1.32 V shows that the product is porphyrin cation radical (Ru(O)2TMP+.). Electrogenerated Ru(O)2TMP+. reacts with styrene to give phenylaectaldehyde (95%) and benaldehyde (5%). This is the first case to oxidize styrene by ruthenium porphyrin electrochemically. The electrolysis products are quite different from those obtained from chemical oxidants.