Reactions of coordinated molecules. 10. The preparation and characterization of several metallo-.beta.-diketone molecules as enol tautomers and as complexes of the enolate anions
Reactions of coordinated molecules. 10. The preparation and characterization of several metallo-.beta.-diketone molecules as enol tautomers and as complexes of the enolate anions
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配位分子的反应。
DOI：
10.1021/ja00455a026
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发表时间：
1977
影响因子：
15
通讯作者：
J. V. Zeile
中科院分区：
文献类型：
--
作者：
C. Lukehart;J. V. Zeile
本文报道了五种金属-β-二酮烯醇互变异构体M [C（CH_3）_0-H-0 C（R）]的合成。金属部分M是ds-（OC）4 Re或r15-C5 H5（OC）Fe，取代基R是甲基、异丙基、苄基或二苯基甲基。还报道了通过将相应的烯醇阴离子配位到Al（III）离子上而得到的三螯合物的制备。详细讨论了几种铝配合物的核磁共振谱。当R不是甲基，M是铁原子时，不对称的三螯合铝配合物表现出螯合环取代基和铁原子配体的顺反异构性。该配合物的结构特征为金属-乙酰丙酮分子的烯醇互变异构体，其中乙酰丙酮的次甲基被m-（OC）4 Re取代。1
The preparation of five metallo-^-diketone molecules as the enol tautomers, M [C (CH3) 0—H—0C (R)], is reported. The metallo moiety, M, is either ds-(OC) 4Re or rj5-C5H5 (OC) Fe, and the substituent, R, is either methyl, isopropyl, benzyl, or diphenylmethyl. The preparation of the tris-chelate complexes obtained by coordinating the corresponding enolate anions to AI (III) ion is reported also. The NMR spectra of several of these aluminum complexes are discussed in detail. When R is not methyl and M is the iron moiety, the unsymmetrical tris-chelate aluminum complexes exhibit cis-trans isomerism of both the chelate-ring substituents and the iron-cyclopentadienyl ligands.We recently reported the preparation of the first example of a metallo-/3-diketone molecule, ds-(OC) 4Re [C (CH3)-O—H—OC (CH3)], 1. This complex was structurally characterized as the enol tautomer of a metallo-acetylacetone mol-ecule where the methine group of acetylacetone is replaced formally by the m-(OC) 4Re moiety. 1