REACTIONS OF ZR(ETA-6-BENZENE)(ALCL4)2 WITH ALKYNES - CYCLOOLIGOMERIZATION REACTIONS AND CRYSTAL AND MOLECULAR-STRUCTURE OF THE 7-MEMBERED METALLACYCLE [ZRCPH(CPH)4CPH][(MU-CL)2ALCL2]2
REACTIONS OF ZR(ETA-6-BENZENE)(ALCL4)2 WITH ALKYNES - CYCLOOLIGOMERIZATION REACTIONS AND CRYSTAL AND MOLECULAR-STRUCTURE OF THE 7-MEMBERED METALLACYCLE [ZRCPH(CPH)4CPH][(MU-CL)2ALCL2]2
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DOI：
10.1021/om00050a019
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发表时间：
1991-04-01
期刊：
影响因子：
2.8
通讯作者：
WURST, K
中科院分区：
文献类型：
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作者：
CALDERAZZO, F;PAMPALONI, G;WURST, K
Zr（II）络合物Zr（eta-6-benzene）（AlCl 4）2（1）的苯溶液在室温下催化2-丁炔环三聚成六甲基杜瓦苯（HMDB）和六甲基二苯（HMB）。 HMDB是主要的初始产物，随后其异构化为HMB。 将二苯乙炔与芳烃锆（Ⅱ）配合物反应，得到标题金属配合物，用X射线衍射方法研究了其晶体和分子结构。 对于[activated ZrCPh（CPh）4CPh][（mu-Cl）2AlCl 2]2，C42H30Al2Cl8Zr.0.5C7H16，M（r）= 1013.6，单斜晶系，空间群P2（1）/n，a = 14.784（2）埃，B = 16.390（2）埃，c = 22.984（2）埃，β = 107.17（1）-度，Z = 4，V = 5321（14）埃3，D（计算）= 1.265 g cm-3，平均透射因子0.989，μ = 60.5 cm-1。 该结构由包括锆的七元环组成，后者的配位层由来自两个AlCl 4基团的四个氯原子完成。
Benzene solutions of the Zr(II) complex Zr(eta-6-benzene)(AlCl4)2 (1) catalyze the cyclotrimerization of 2-butyne to hexamethyl Dewar benzene (HMDB) and hexamethylbenzene (HMB) at room temperature. HMDB is the predominant initial product, followed by its isomerization to HMB. When diphenylacetylene was reacted with the (arene)zirconium(II) complex, the title metallacycle derivative was obtained, whose crystal and molecular structure was studied by X-ray diffraction methods. For [activated ZrCPh(CPh)4CPh][(mu-Cl)2AlCl2]2, C42H30Al2Cl8Zr.0.5C7H16, M(r) = 1013.6, monoclinic, space group P2(1)/n, a = 14.784 (2) angstrom, b = 16.390 (2) angstrom, c = 22.984 (2) angstrom, beta = 107.17 (1)-degrees, Z = 4, V = 5321 (14) angstrom 3, D(calc) = 1.265 g cm-3, average transmission factor 0.989, and mu = 60.5 cm-1. The structure consists of a seven-membered cycle including zirconium, the coordination sphere of the latter being completed by four chlorine atoms from the two AlCl4 groups.