The Crystal and Molecular Structure of Dimeric Bis(acetylacetonato)aquocobalt(II) and the Preparation of Some Other New Hydrates
The Crystal and Molecular Structure of Dimeric Bis(acetylacetonato)aquocobalt(II) and the Preparation of Some Other New Hydrates
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二聚双(乙酰丙酮)水合钴(II)的晶体和分子结构以及其他一些新水合物的制备
DOI：
10.1021/ic50037a020
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发表时间：
1966
影响因子：
4.6
通讯作者：
R. C. Elder
中科院分区：
文献类型：
--
作者：
F. Cotton;R. C. Elder
双（乙酰丙酮）钴-(II) Co (AA) 2的溶液化学相当复杂。钴实现六配位的趋势是明显的，并且似乎是控制这些体系行为的最重要的单一结构原则。在供体溶剂中，乙酰丙酮与两个供体分子D反应生成八面体配合物Co (AA) 2D2。在非配位溶剂中，光谱研究表明Co (AA) 2在极稀溶液中以四面体单体存在；光谱学和低温学证据表明：(1)(a)得到国家科学基金会的资助；(b)国家卫生研究院博士前研究员，1962-1964年。(2)王志强，王志强。， 12, 703（1959）。(3)科顿和霍尔姆。化学。Soc。， 82, 2979（1960）。(4)(a) f.a. Cotton和RH Soderberg， Inorg。化学。， 3,1（1964年）；(b) DP Graddon, Nature, 195,891（1962）。通过聚合可以分离出一种新的化合物，这种化合物可以在更浓的溶液中得到八面体配位。聚合也被证明发生在升华形成的固体[Co (AA) 2] 4中。如果在非配位溶剂的聚合物溶液中加入少量中性供体配体D，则建立络合物平衡，并可从这些溶液中得到以下类型的化合物：[Co-(AA) 2] 4,[Co (AA) 2] 2D,[Co (AA) 2D] 2和Co (AA) 2D2，其中D可以是水，吡啶，6或环己胺。当试图结晶一致的anhy-(5) FA棉花和RC Elder， Inorg。化学。， 4, 1145（1965）。需要强调的是，在固体中发现了四聚体，而据报道，溶液中含有二聚体4a或三聚体。这一点将在本系列后面的文章中讨论。
Introduction The solution chemistry of bis (acetylacetonato) cobalt-(II), Co (AA) 2, is rather complex. The tendency of the cobalt to achieve six-coordination is pronounced and appears to be the most important single structural prin-ciple governing the behavior of these systems. In donor solvents, the bis (acetylacetonate) reacts with two donor molecules, D, to foim the octahedral com-plex, Co (AA) 2D2. 2, 3 In noncoordinating solvents, spec-troscopic43 studies have shown that Co (AA) 2 exists as a tetrahedral monomer in very dilute solution; both spectroscopic43 and cryoscopic4b evidence indicate that (1)(a) Supported by a grant from the National Science Foundation;(b) National Institutes of Health Predoctoral Fellow, 1962-1964.(2) G. J. Bullen, Acia Cryst., 12, 703 (1959).(3) FA Cotton and RH Holm, J. Am. Chem. Soc., 82, 2979 (1960).(4)(a) F. A. Cotton and RH Soderberg, Inorg. Chem., 3, 1 (1964);(b) DP Graddon, Nature, 195, 891 (1962). been isolated as well as a new compound which may be either in more concentrated solutions octahedral coordination is achieved through polymerization. Polymerization has also beenshown to occur in the solid [Co (AA) 2] 4 formed by sublimation. 5 If a small amount of some neutral donor ligand, D, is introduced into a solution of polymer in a noncoordinating solvent, complex equi-libria are established and the following typesof com-pounds can be obtained from such solutions:[Co-(AA) 2] 4,[Co (AA) 2] 2D,[Co (AA) 2D] 2, and Co (AA) 2D2, where D may be water, pyridine, 6 or cyclohexylamine. 7 While attempts to crystallize consistently an anhy-(5) FA Cotton and RC Elder, Inorg. Chem., 4, 1145 (1965). It is to be emphasized that tetramers were found in the solid, whereas the solutions were reported to contain either dimers4a or trimers. 4b This point will be discussed in a later paper in this series.