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本文用自旋捕捉技术与ESR相结合的方法,研究四羰基二氯二铑和八种顺二羰基(二齿N-配体)铑(Ⅰ)四苯硼酸盐配合物光解的活泼中间体.结果表明,四羰基二氯二铑光解初级过程是Rh—Rh键的均裂,产生Rh中心自由基,并可为PBN,ND及TBN捕获.顺二羰基(二齿N-配体)铑(Ⅰ)四苯硼酸盐配合物光解的初级阶段,产生的都是Bph_4~-阴离子分解的Ph·自由基,且随着配体为氮杂环,苯胺环,及吡啶环,阳离子稳定性降低.
In this paper, the spin-capture technology and ESR combined with the method to study the four carbonyl dichloro-rhodium and eight cis dicarbonyl (bidentate N- ligand) rhodium (I) tetraphenylborate complex photolytic active intermediate The results showed that the primary photolysis reaction of tetracarbonyl dichlorodifluoride was the cleavage of Rh-Rh bond, resulting in the production of Rh center and the capture of PBN, ND and TBN.The cis-dicarbonyl (bidentate N-ligand ) Rhodium (Ⅰ) tetraphenylborate complex at the initial stage of photolysis, resulting in the decomposition of Bph_4 ~ - anion Ph · radical, and with the ligands for the nitrogen heterocycle, aniline ring, and pyridine ring, Cationic stability is reduced.