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脂肪胺氮氧化物特别是(CH_3)_3NO作为氧转移试剂已在金属有机合成中得到广泛应用,其反应动力学与机理近年来也进行了系统研究.相比之下,人们对氧化吡啶及有关的芳香胺氮氧化物作为氧转移试剂的了解却显得十分有限.有关其在金属有机化学中的应用研究未见文献报道.为此,本文选择了九种取代的吡啶氮氧化物作为氧转移试剂,以混配的金属羰基化合物[(η~5-C_5H_5)Fe(CO)_3]PF_6作为反应底物,研究了两者在外加配体PPh_3存在下发生氧原子转移反应的动力学与机理.定量比较了九种试剂的氧转移活性大小,考察了反应活性与取代基效应、试剂碱性、N—O键伸缩振动频率之间的关系.
Aliphatic amine nitrogen oxides, especially (CH_3) _3NO as oxygen transfer reagents have been widely used in metal-organic synthesis, and their reaction kinetics and mechanism have been systematically studied in recent years.In contrast, people on the oxidation of pyridine and related Of the aromatic amine nitrogen oxides as oxygen transfer reagent is very limited understanding of its application in metal organic chemistry has not been reported in the literature.Therefore, nine substituted pyridine nitrogen oxides were selected as the oxygen transfer reagent The kinetics and mechanism of oxygen atom transfer reaction in the presence of the PPh_3 ligand were studied with mixed metal carbonyl [(η5-C_5H_5) Fe (CO) _3] PF_6 as reaction substrate. Quantitatively, the oxygen transfer activities of nine reagents were compared, and the relationship between the reaction activity and substituent effect, reagent basicity and stretching vibration frequency of N-O bond was investigated.