The unpredictable structural features of chromium(II) pyrrolyls: synthesis and x-ray structures of monomeric square-planar (.eta.1-2,5-Me2C4H2N)2Cr(py)2, square-pyramidal (.eta.1-C4H4N)2Cr(py)3, dimeric [(7-azaindolyl)2Cr(DMF)]2, and polymeric [(.eta.1-2,5-Me2C4N2)4CrNa2(THF)2(Et2O)]n. An aborted Cr
The unpredictable structural features of chromium(II) pyrrolyls: synthesis and x-ray structures of monomeric square-planar (.eta.1-2,5-Me2C4H2N)2Cr(py)2, square-pyramidal (.eta.1-C4H4N)2Cr(py)3, dimeric [(7-azaindolyl)2Cr(DMF)]2, and polymeric [(.eta.1-2,5-Me2C4N2)4CrNa2(THF)2(Et2O)]n. An aborted Cr
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吡咯铬(II)不可预测的结构特征：单体方形平面(.eta.1-2,5-Me2C4H2N)2Cr(py)2、方形锥体(.eta.1-C4H4N)的合成和X射线结构
DOI：
10.1021/ic00336a022
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发表时间：
1990
影响因子：
4.6
通讯作者：
W. Smeets
中科院分区：
文献类型：
--
作者：
J. J. Edema;S. Gambarotta;A. Meetsma;Fre Van Bolhuis;A. Spek;W. Smeets
分别为THF(1)，py(2)]和(i，1-2，5-Me 2 C 4 H 2 N) 2 Cr(L) 2 [L＝THF(4)，py(5)]。通过X射线衍射分析解析了2和5的晶体结构。尽管配体之间相似，但这两种单体配合物具有明显不同的结构：2具有不寻常的方锥体几何形状，而5是方形平面，分别具有金属的低自旋和高自旋电子构型。晶体数据如下（'= 130 K，Mo Ka，= 0.71073 A）：2，三斜晶系，空间群 P\，a= 9.153 (4) A，b= 10.659 (2) A，c= 13.707 (3) A，a= 86.01 (1)，ß= 82.93 (3)，y= 88.65 (2) 6，Z= 2. 5，三斜晶系，空间群 P\，a= 6.986 (2) A，6= 8.812 (2) A，c= 9.018 (3) A，a= 87.09 (2)，ß= 68.95 (2)，= 83.18 (2)，Z= 1。当供体原子连接到其中之一时，观察到二聚化吡咯基配体的两个a位，恢复了三中心螯合配体的独特几何形状。通过X射线衍射分析证明了[(7-氮杂吲哚基)2Cr-(DMF)]2-2DMF (7)(DMF=AUV-二甲基甲酰胺)的二聚结构。 7 的晶体数据：单斜晶系，空间群 72,/d，a= 9.458 (1) A，b= 19.085 (2) A，c= 11.850 (1) ß= 109.92 (1)，Z= 2 磁性和结构特征 [Cr-Cr= 2.604 (2) A] 表明不存在 Cr-Cr 四重键。 1 和 4 与 2 当量的 C4H4NNa 和 2, 5-Me2C4H2NNa 的反应分别导致形成稳定的聚合铬酸盐 [(C4H4N) 4CrNa2L3]„(3) 和 [(2, 5-Me2C4H2N) 4CrNa2L3]„(6)。[L= Et2O、二恶烷、THF]。聚合物聚集，在6的情况通过X射线结构测定，是通过吡咯基配体与来自两个不同的t(V-吡咯基) 4Cr] 2" 片段的Na阳离子的相互作用来实现的。 6 (7= 130 K, Mo= 0.71073 A) 的晶体数据如下：单斜晶系，空间群 72，a= 9.045 (1) A，b= 15.285 (1) k，c= 13.621 (1) A，ß= 97.42 (1)，Z= 2。
THF (1), py (2)] and (i, l-2, 5-Me2C4H2N) 2 Cr (L) 2 [L= THF (4), py (5)], respectively. The crystal structures of 2 and 5 were solvedby X-ray diffraction analyses. In spite of the similarity between the ligands, the two monomeric complexes possess remarkably different structures: 2 has an unusual square-pyramidal geometry, while 5 is square-planar with low-and high-spin electronic configurations of the metal, respectively. Crystal data are as follows ('= 130 K, Mo Ka,= 0.71073 A): 2, triclinic, space group P\, a= 9.153 (4) A, b= 10.659 (2) A, c= 13.707 (3) A, a= 86.01 (1), ß= 82.93 (3), y= 88.65 (2) 6, Z= 2. 5, triclinic, space group P\, a= 6.986 (2) A, 6= 8.812 (2) A, c= 9.018 (3) A, a= 87.09 (2), ß= 68.95 (2),= 83.18 (2), Z= 1. Dimerization was observed when a donor atom, attached to one of the two a positions of the pyrrolyl ligands, restored the unique geometry of the three-center chelating ligands. The dimeric structure of [(7-azaindolyl) 2Cr-(DMF)] 2-2DMF (7)(DMF= AUV-dimethylformamide) was demonstrated by X-ray diffraction analysis. Crystal data for 7: monoclinic, space group 72,/d, a= 9.458 (1) A, b= 19.085 (2) A, c= 11.850 (1) ß= 109.92 (1), Z= 2 Magnetic properties and structural features [Cr-Cr= 2.604 (2) A] suggest the absence of a Cr-Cr quadruple bond. Reaction of 1 and 4 with 2 equiv of C4H4NNa and 2, 5-Me2C4H2NNa leads respectively to the formation of stable polymeric chromates [(C4H4N) 4CrNa2L3]„(3) and [(2, 5-Me2C4H2N) 4CrNa2L3]„(6).[L= Et20, dioxane, THF]. The polymeric aggregation, demonstrated in the case of 6 by an X-ray structure determination, is achievedvia a r interaction of the pyrrolyl ligands with the Na cations from two different t (V-pyrrolyl) 4Cr] 2" fragments. Crystal data for 6 (7= 130 K, Mo= 0.71073 A) are as follows: monoclinic, space group 72,, a= 9.045 (1) A, b= 15.285 (1) k, c= 13.621 (1) A, ß= 97.42 (1), Z= 2.