COPPER(II) COMPLEXES OF SUBSTITUTED MACROBICYCLIC HEXAAMINES - COMBINED TRIGONAL AND TETRAGONAL DISTORTIONS
COPPER(II) COMPLEXES OF SUBSTITUTED MACROBICYCLIC HEXAAMINES - COMBINED TRIGONAL AND TETRAGONAL DISTORTIONS
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DOI：
10.1021/ic00118a005
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发表时间：
1995-07-05
影响因子：
4.6
通讯作者：
WHITE, AH
中科院分区：
文献类型：
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作者：
BERNHARDT, PV;BRAMLEY, R;WHITE, AH
合成了六胺络合物 [M{(NH3)(2)sar}](4+) 和 [M{(NMe(3))(2)sar}](4+) (M = Cu(II), Zn(II); sar = 3,6,10,13,16,19-六氮杂双环[6.6.6]二十烷)，并进行了光谱和结构表征。 [Cu{(NH3)(2)sar}](NO3)(4) 的 X 射线晶体结构分析。 H2O（单斜晶系，P2(1)，a 12.311(3) Angstrom，b 12.338(4) Angstrom，c 8.574(3) Angstrom，β 93.91(3) 度，Z = 2)，[Zn{(NH3)(2)sar}](NO3)(4) 。 H2O（单斜晶系，P2(1)，a 12.365(4) Angstrom，b 12.396(7) Angstrom，c 8.587(4) Angstrom，beta 94.13(3)°，Z = 2)，[Cu{(NMe(3))(2)sar}](ClO4)(4)（六方晶系，a报道了 8.689(2) Angstrom，c 27.927(2) Angstrom，Z = 2) 和 [Zn{(NMe(3))(2)sar}](ClO4)(4) （六方晶系， ， 8.669(5) Angstrom，c 27.998(5) Angstrom，Z = 2)。可见光-近红外吸收、圆二色性、磁圆二色性和电子顺磁共振光谱研究揭示了扭曲的 CuN6 发色团。三角畸变是由配体的空间要求引起的，而四方畸变是由 Cu(II) 配合物中的 Jahn-Teller 耦合引起的。这些铜 (II) 配合物的 X 射线晶体学研究揭示了由于每个晶格中静态无序和动态过程的结果，部分平均 ([CU{(NH3)(2)sar}](4+)) 和完全平均 ([Cu{(NMe(3))(2)sar}](4+)) 几何形状。 [Cu{(NMe(3))(2)sar}](4+) 部分拆分为其对映体形式，得到第一个稳定的手性分子，其中 Cu(II) 是立体原子。在缺乏 Cu(II) 相关物的 Jahn-Teller 耦合特征的情况下，类似的 Zn(IT) 配合物在溶液和固态中均表现出高度对称性结构。
The hexaamine complexes [M{(NH3)(2)sar}](4+) and [M{(NMe(3))(2)sar}](4+) (M = Cu(II), Zn(II); sar = 3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane) have been synthesized and characterized both spectroscopically and structurally. X-ray crystal structural analyses of [Cu{(NH3)(2)sar}](NO3)(4) . H2O (monoclinic,P2(1), a 12.311(3) Angstrom, b 12.338(4) Angstrom, c 8.574(3) Angstrom, beta 93.91(3)degrees, Z = 2), [Zn{(NH3)(2)sar}](NO3)(4) . H2O (monoclinic, P2(1), a 12.365(4) Angstrom, b 12.396(7) Angstrom, c 8.587(4) Angstrom, beta 94.13(3)degrees, Z = 2), [Cu{(NMe(3))(2)sar}](ClO4)(4) (hexagonal , a 8.689(2) Angstrom, c 27.927(2) Angstrom, Z = 2), and [Zn{(NMe(3))(2)sar}](ClO4)(4) (hexagonal, , a 8.669(5) Angstrom, c 27.998(5) Angstrom, Z = 2) are reported. Visible-near-infrared absorption, circular dichroism, magnetic circular dichroism, and electron paramagnetic resonance spectroscopic studies reveal distorted CuN6 chromophores. Trigonal distortions arise from steric requirements of the ligands, whereas tetragonal distortions result from Jahn-Teller coupling in the Cu(II) complexes. X-ray crystallographic studies of these copper(II) complexes revealed partially averaged ([CU{(NH3)(2)sar}](4+)) and completely averaged ([Cu{(NMe(3))(2)sar}](4+)) geometries as a result of both static disorder and dynamic processes throughout each lattice. Partial resolution of [Cu{(NMe(3))(2)sar}](4+) into its enantiomeric forms was achieved to give the first stable chiral molecule where Cu(II) is the stereogenic atom. In the absence of Jahn-Teller coupling characteristic of their Cu(II) relatives, the analogous Zn(IT) complexes exhibited high-symmetry structures both in solution and in the solid state.