Synthesis, Spectroscopy, and Novel Reactivity of Metalloporphyrin Compounds

一种极其重要的化学反应是将氧原子加到有机化合物中，这一过程被称为氧化。本研究项目所研究的金属卟啉化合物是进行生物氧化的酶的活性位点，作为实验室和工业氧化反应的催化剂也有很大的前景。该项目的目的包括合成这类新化合物，并对催化作用的机制有更深入的了解。这个项目在一定程度上代表了目前在高度氧化和不寻常的金属卟啉化合物的光谱研究的一般领域的努力的继续。新提出的研究旨在展示碳氢化合物和羰基化合物氧化的原型化学和电化学系统。用铁卟啉催化空气氧化这些分子的初步结果特别值得注意。顺磁性和通常高度反应的金属卟啉化合物的氘核磁共振波谱为这里描述的五个不同项目提供了一个中心主题。具体目标包括：(1)继续强氧化性氧阴离子和硫阴离子轴向配体金属卟啉配合物的合成和反应性研究；(2)氟铁配合物在电催化烃类氧化和双氧活化中的广泛应用；(3)详细研究了氯(I)氧化物作为金属卟啉氧化剂，并评价了该酸酐在锰卟啉介导的次氯酸盐氧化烃类化合物中的作用；(4)评价各种金属卟啉衍生物作为醛类和其他共底物空气氧化催化剂的作用；(5)在烷基卟啉配合物和芳烯铁卟啉配合物的铁碳键上插入底物，合成新型金属卟啉化合物。

An extremely important type of chemical reaction is the addition of oxygen atoms to an organic compound, a process called oxidation. The compounds under study in this research project, metalloporphyrins, constitute the active sites of enzymes which carry out biological oxidations and also show great promise as laboratory and industrial catalysts for oxidation reactions. The aims of this project include both the synthesis of new compounds of this type and achieving a more profound understanding of the mechanisms of catalytic action. This project represents in part a continuation of present efforts in the general area of spectroscopic studies of highly oxidized and unusual metalloporphyrin compounds. Newly proposed studies are designed to demonstrate prototype chemical and electrochemical systems for oxidation of hydrocarbon and carbonyl compounds. Preliminary results with iron porphyrin-catalyzed air oxidation of these molecules are particularly noteworthy. Deuterium NMR spectroscopy of the paramagnetic and often highly reactive metalloporphyrin compounds provides a central theme for the five diverse projects described here. Specific objectives include: (1) continued synthetic and reactivity studies of metalloporphyrin complexes with strongly oxidizing oxyanion and thioanion axial ligands; (2) expanded use of fluoroiron complexes for electrocatalytic hydrocarbon oxidations and dioxygen activation; (3) detailed study of chlorine(I) oxide as a metalloporphyrin oxidant, and evaluation of the role of this anhydride in manganese porphyrin mediated hypochlorite oxidation of hydrocarbon compounds; (4) evaluation of various metalloporphyrin derivatives as catalysts for the air oxidation of aldehydes and other cosubstrates; and (5) synthesis of novel metalloporphyrin compounds by insertion of substrates into the iron-carbon bond of alkyl and aryliron porphyrin complexes.