Structure of hexakis(N-methylimidazole-N')iron(II) tetraphenylborate dichloromethane solvate.
Structure of hexakis(N-methylimidazole-N')iron(II) tetraphenylborate dichloromethane solvate.
复制标题
六(N-甲基咪唑-N)四苯基硼酸铁(II)二氯甲烷溶剂化物的结构。
DOI：
10.1107/s0108270188012211
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发表时间：
1989
期刊：
影响因子：
--
通讯作者：
KurtzJr,DM
中科院分区：
文献类型：
--
作者：
Miller,LL;Jacobson,RA;Chen,YS;KurtzJr,DM
[Fe (C4H6N2) 6][B (C6H5) 4]CH2CI2, Mr= 1271.88，单斜，P21/c, a= 20.5320 (6), b= 15.113 (3), c= 23.611 (7) a, fl= 109.01 (3)， V= 6926.9 (1)/~ 3, Z—4,Dx= 1.23 g cm-3, g (Mo Ka)= 0.70966 a，石墨单色器，~= 3.37 cm-~, F (000)= 2680， T= 298 K， R= 0.057。不对称单元由一个[Fe (C4H6N2) 6] 2+阳离子、两个不同的BPh4阴离子和一个CH2CI2组成。铁原子由六个n -甲基咪唑配体八面配位。每个阳离子的6个Fe—N键距离从2.174 （1 l）到2.228(10)/~，平均为2.207 (12)a，这一平均距离在高自旋铁配合物的范围内。n -甲基咪唑配体相互反立的环面夹角分别为17.56、18.48和157.56。这些环面近似平行或垂直于赤道Fe-N键。该化合物的所有制备过程均在氩气气氛下进行。将十倍摩尔过量的n -甲基咪唑加入无水FeC13无水乙醇溶液中。回流1 ha后，将超过铁的两摩尔的NaBPh4加入冷却的溶液中，形成黄红色的固体，将其洗涤并真空干燥。该固体溶解于含有过量n -甲基咪唑的四氢呋喃中，通过滴加（Me2Si） 2S还原，形成白色结晶固体。该固体由二氯甲烷-己烷重结晶得到分析纯的[Fe (CaH6N2) 6](BPh4) 2。CH2C12。用FeC1E反应制备了相同的化合物。在乙醇中加入4H20和过量的n -甲基咪唑，然后与NaBPh4进行复分解并重新结晶（Wu & Kurtz Jr，未发表的结果）。将一个尺寸约为0.10 x 0.12 x 0.15 mm的无色单晶安装在Lindemann-glass毛细管中，在Ar条件下，用自动标引程序ALICE指示单斜对称
[Fe (C4H6N2) 6][B (C6H5) 4] 2. CH2CI2, Mr= 1271.88, monoclinic, P21/c, a= 20.5320 (6), b= 15.113 (3), c= 23.611 (7) A, fl= 109.01 (3), V= 6926.9 (1)/~ 3, Z--4, Dx= 1.23 g cm-3, g (Mo Ka)= 0.70966 A, graphite monochromator,~= 3.37 cm-~, F (000)= 2680, T= 298 K, R= 0.057 for 2310 unique observed reflections. The asymmetric unit consists of a single [Fe (C4H6N2) 6] 2+ cation, two distinct BPh4 anions, and one CH2CI2. The Fe atom is octahedrally coordinated by six N-methylimidazole ligands. The six Fe--N bond distances per cation range from 2.174 (1 l) to 2.228 (10)/~,, the average being 2.207 (12) A. This average distance is within the range previously ob-served for high-spin ferrous complexes. The ring planes of N-methylimidazole ligands that lie trans to each other have interplane angles of 17.56, 18.48 and 157.56. These ring planes lie approximately either parallel or perpendicular to equatorial Fe-N bonds.Experimental. All procedures for preparation of the compound were performed under an Ar atmosphere. A tenfold molar excess of N-methylimidazole was added to a solution of anhydrous FeC13 in absolute ethanol. After refluxing for 1 ha twofold molar excess over Fe of NaBPh4 was added to the cooled solution, resulting in the formation of a yellowish-red solid, which was washed and vacuum dried. This solid was dissolved in THF containing excess N-methylimidazole and reduced by dropwise addition of (Me2Si) 2S, which resulted in the formation of a white crystalline solid. This solid was recrystallized from dichloromethane-hexanes to give analytically pure [Fe (CaH6N2) 6](BPh4) 2. CH2C12. The identical compound has since been prepared by reaction of FeC1E. 4H20 and excess N-methylimidazole in etha-nol followed by metathesis with NaBPh4 and re-crystallization (Wu & Kurtz Jr, unpublished results). A colorless single crystal of approximate dimensions 0.10 x 0.12 x 0.15 mm was mounted in a Lindemann-glass capillary under Ar. Monoclinic synlmetry was indicated by the automatic indexing routine ALICE