SOME TETRAGONAL COBALT(III) COMPLEXES CONTAINING TETRADENTATE MACROCYCLIC AMINE LIGANDS WITH DIFFERENT DEGREES OF UNSATURATION
SOME TETRAGONAL COBALT(III) COMPLEXES CONTAINING TETRADENTATE MACROCYCLIC AMINE LIGANDS WITH DIFFERENT DEGREES OF UNSATURATION
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DOI：
10.1021/ic50118a008
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发表时间：
1972-01-01
影响因子：
4.6
通讯作者：
FARMERY, K
中科院分区：
文献类型：
--
作者：
JACKELS, SC;BUSCH, DH;FARMERY, K
在特定条件下的缩合反应生成了一系列钴与两个新的大环配体的配合物，它们的不饱和程度不同，加氢反应得到了一系列相关的全饱和配体的衍生物。它们都是14元大环，含有4个氮给体；TIM有4个亚胺基团；DIM、2个亚胺和2个仲胺；以及DMC，4个胺。报道了系列钴(III)配合物的合成、结构和性质，其中X-=卤化物或NO2-，Y-=卤化物、CIO、-或PF6-。红外和PMR光谱研究为这些化合物中大环配体的结构提供了证据，而后者则为这些化合物之间的立体化学关系提供了洞察力。光谱化学研究表明，大环的配位场强度随着配体不饱和度的增加而增加。与其他大环的比较表明，-N(H)-、N=C、-N=C-C=N-和py等基团对配位场强度的相对影响。伏安数据清楚地表明，配体不饱和度越高，钴的低氧化态越稳定。
Condensation reactions under highly specific conditions have yielded series of cobalt complexes with two new macrocyclic ligands that vary in the extent of their unsaturation, and hydrogenation has given a related series of derivatives of a fully saturated ligand. All are 14-membered macrocycles containing four nitrogen donors; TIM has4 imine groups; DIM, 2 imines and 2 secondary amines; and DMC, 4 amines. The syntheses, structures, and properties of the resulting series of cobalt (III) complexes, ízcreí-[Co (TIM) X2] Y, trans-[Co (DIM) Xj] Y, and trans-[Co (DMC) X2] Y, are reported for X-= halide or NO2-and Y-= halide, CIO.,-, or PF6-. Infrared andpmr spectral studies provide proof of the structures of the macrocyclic ligands in these compounds and the latter has given insight into stereochemical relationships among these com-plexes. Spectrochemical studies reveal that the ligand field strengths of the macrocyclesincrease as the degree of unsatura-tion of the ligand increases. Comparisons with other macrocyclesshow the relative effect on ligand field strengths of such groups as-N (H)-, N= C,-N= C—C= N-, and py. Voltametric data show clearly that the lower oxidation states ofcobalt are stabilized by greater degrees of ligand unsaturation.