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SYNTHETIC UTILITY OF CHROMIUM(II)/(III) AND COBALT(II)/(III) REDOX CHEMISTRY MEDIATED BY COORDINATED LIGANDS (AGOSTIC, GLUCOSE TOLERANCE, CARBON-HYDROGEN ACTIVATION).

机译：协同配位体介导的铬（II）/（III）和钴（II）/（III）氧化还原化学的合成效用（农业，葡萄糖耐量，碳氢活化）。

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The reactivity of transition metal ions can be greatly influenced by coordinated ligands either through electronic or steric factors. The redox chemistry of M(II)/M(III) where M = Co and Cr has provided extensive information on the behavior of transition metals due to the kinetic inertness of the trivalent state. The slow substitution rates of Co(III) and Cr(III) have allowed detailed investigations of reaction products and intermediates which effectively are "snapshots" of reaction pathways. In this investigation it was found that by appropriate balance of steric and electronic factors associated with coordinated ligands and the M(II)/M(III) redox couples, new insights into cobalt and chromium chemistry were obtained. The results could make a significant impact on the role of metal ions in biological systems and in industrial catalysis.;A synthetic technique for producing stable nitrogen coordinated Cr(III)-nicotinic acid complexes was developed by taking advantage of the poised intramolecular redox couple which exists between Cr(II) and (nitrogen coordinated) nicotinic acid. This method, which we have termed "ligand reduction redox trapping," is not a generally new synthetic technique, but the application to Cr(III)-nicotinic acid complexes may prove very useful since Cr(III) in conjunction with nicotinic acid has been implicated in the maintenance of normal glucose metabolism in mammalian systems.;In the second study, the unique stereochemical requirements of the (coordinated) ligand dacoda (1,5-diazacyclooctane N,N'-diacetic acid) were combined with Co(II)/(III) redox chemistry resulting in intramolecular carbon-hydrogen activation via electrophilic attack of the Co(III) center on the C(2) carbon of the coordinated dacoda ligand. The reaction pathway proceeds via an intermediate containing a three-center, two-electron Co(III)-H-C (agostic) interaction. This system is the first example of a well-characterized, classical Werner-type complex capable of C-H activation and will certainly shed light on the general problem of alkane activation and the role agostic interactions in C-H activation systems.

机译：过渡金属离子的反应性可通过电子或空间因素受配位配体的影响很大。 M（II）/ M（III）（其中M = Co和Cr）的氧化还原化学因三价态的动力学惰性而提供了有关过渡金属行为的广泛信息。 Co（III）和Cr（III）的缓慢取代率使得人们可以详细研究反应产物和中间体，而这些产物和中间体实际上是反应途径的“快照”。在这项研究中，发现通过与配位体和M（II）/ M（III）氧化还原对相关的空间和电子因素的适当平衡，获得了对钴和铬化学性质的新见解。结果可能会对金属离子在生物系统和工业催化中的作用产生重大影响。;利用平衡的分子内氧化还原对，开发了一种生产稳定的氮配位的Cr（III）-烟酸配合物的合成技术。存在于Cr（II）和（氮配位）烟酸之间。这种方法，我们称为“配体还原氧化还原捕获”，不是一种普遍的合成技术，但由于已将Cr（III）与烟酸结合使用，因此在Cr（III）-烟酸络合物中的应用可能非常有用。参与维持哺乳动物系统中正常的葡萄糖代谢。;在第二项研究中，将（配位的）配体dacoda（1,5-二氮环辛烷N，N'-二乙酸）的独特立体化学要求与Co（II）结合使用/（III）氧化还原化学通过配位的达科达配体的C（2）碳上的Co（III）中心的亲电攻击导致分子内的碳氢活化。反应途径是通过含有三中心，两电子的Co（III）-H-C（水合）相互作用的中间体进行的。该系统是具有特征的，能够进行C-H活化的经典Werner型配合物的第一个例子，无疑将阐明烷烃活化的一般问题以及C-H活化系统中的角色异常相互作用。

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作者
BRODERICK, WILLIAM E.;
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Washington State University.;

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授予单位 Washington State University.;
学科 Chemistry Inorganic.
学位 Ph.D.
年度 1986
页码 85 p.
总页数 85
原文格式 PDF
正文语种 eng
中图分类无机化学;
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5. MANGANESE(II) AND COBALT(III) COMPLEXES OF MULTIDENTATE LIGANDS: I. MANGANESE(II) COMPLEXES OF A MACROCYCLIC PENTADENTATE LIGAND. II. COBALT(III) COMPLEXES OF LINEAR TETRAMINE LIGANDS. [D] . HAMILTON, HOBART GORDON, JR. 1968

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SYNTHETIC UTILITY OF CHROMIUM(II)/(III) AND COBALT(II)/(III) REDOX CHEMISTRY MEDIATED BY COORDINATED LIGANDS (AGOSTIC, GLUCOSE TOLERANCE, CARBON-HYDROGEN ACTIVATION).

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