含铝氢键的聚吡唑基铝酸盐配合物。

Poly(pyrazolyl)aluminate complexes containing aluminum-hydrogen bonds.

机构信息

Department of Chemistry, Wayne State University, Detroit, Michigan 48202, United States.

出版信息

Inorg Chem. 2011 Oct 3;50(19):9210-2. doi: 10.1021/ic201541c. Epub 2011 Aug 30.

DOI:10.1021/ic201541c

Abstract

The treatment of LiAlH(4) with 2, 3, or 4 equiv of the 3,5-disubstituted pyrazoles Ph(2)pzH or iPr(2)pzH afforded [Li(THF)(2)][AlH(2)(Ph(2)pz)(2)] (97%), [Li(THF)][AlH(Ph(2)pz)(3)] (96%), [Li(THF)(4)][Al(Ph(2)pz)(4)] (95%), and [Li(THF)][AlH(iPr(2)pz)(3)] (89%). The treatment of ZnCl(2) with [Li(THF)][AlH(Ph(2)pz)(3)] afforded Zn(AlH(Ph(2)Pz)(3))H (70%). X-ray crystal structures of these complexes demonstrated κ(2) or κ(3) coordination of the aluminum-based ligands to the Li or Zn ions. The treatment of [Li(THF)][AlH(Ph(2)pz)(3)] with MgBr(2) or CoCl(2) in THF/Et(2)O solutions, by contrast, afforded the pyrazolate transfer products Mg(2)Br(2)(Ph(2)pz)(2)(THF)(3)·2THF (25%) and Co(2)Cl(2)(Ph(2)pz)(2)(THF)(3)·THF (23%) as colorless and blue crystalline solids, respectively. An analogous treatment of [Li(THF)][AlH(Ph(2)pz)(3)] with MCl(2) (M = Mn, Fe, Ni, Cu) afforded metal powders and H(2), illustrating hydride transfer from Al to M as a competing reaction path.

摘要

用 2、3 或 4 当量的 3、5-取代吡唑 Ph(2)pzH 或 iPr(2)pzH 处理 LiAlH(4)，得到 [Li(THF)(2)][AlH(2)(Ph(2)pz)(2)]（97%）、[Li(THF)][AlH(Ph(2)pz)(3)]（96%）、[Li(THF)(4)][Al(Ph(2)pz)(4)]（95%）和[Li(THF)][AlH(iPr(2)pz)(3)]（89%）。用 [Li(THF)][AlH(Ph(2)pz)(3)]处理 ZnCl(2)，得到 Zn(AlH(Ph(2)Pz)(3))H（70%）。这些配合物的 X 射线晶体结构表明，铝基配体与 Li 或 Zn 离子呈 κ(2)或 κ(3)配位。相比之下，用 MgBr(2)或 CoCl(2)在 THF/Et(2)O 溶液中处理[Li(THF)][AlH(Ph(2)pz)(3)]，得到无色和蓝色结晶固体的吡唑转移产物 Mg(2)Br(2)(Ph(2)pz)(2)(THF)(3)·2THF（25%）和 Co(2)Cl(2)(Ph(2)pz)(2)(THF)(3)·THF（23%）。用 MCl(2)（M = Mn、Fe、Ni、Cu）类似地处理[Li(THF)][AlH(Ph(2)pz)(3)]，得到金属粉末和 H(2)，说明 Al 到 M 的氢化物转移是一个竞争反应途径。