tricyano(N,N',N''-trimethyl-1,4,7-triazacyclononane-κ3N)chromium(III) | 305801-31-4

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: tricyano(N,N',N''-trimethyl-1,4,7-triazacyclononane-κ3N)chromium(III)
• 英文别名: (1,4,7-trimethyl-1,4,7-triazacyclononane)Cr(CN)3；[(Me3tacn)Cr(CN)3]；[(N,N',N''-trimethyl-1,4,7-triazacyclononane)Cr(CN)3]；Cr(cyanide)3(Me3tacn)
• CAS: 305801-31-4
• 化学式: C₁₂H₂₁CrN₆
• 分子量: 301.335
• InChiKey: RCXPWQKEESGDQX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  tricyano(N,N',N''-trimethyl-1,4,7-triazacyclononane-κ3N)chromium(III) 、 [(N,N',N''-trimethyl-1,4,7-triazacyclononane)Cu(H2O)2](ClO4)2 以 乙醇 、 乙腈 为溶剂， 以72%的产率得到[(Me3tacn)3Cu3Cr2(CN)6](ClO4)6
  参考文献：
  名称：

  基于三角双锥几何的高自旋 Ni3Fe2(CN)6 和 Cu3Cr2(CN)6 团簇

  摘要：

  两种新型氰基桥簇化合物的合成和表征，(Tp2(cyclen)3Ni II 3Fe III 2(CN)6)(BF4)4 (1) 和 ((Me3tacn)5Cu II 3Cr III 2(CN)6) (ClO4)6 (2), 报道。每个簇的结构都基于三角双锥几何，并且成分金属离子之间的铁磁耦合显示分别产生S 4a 和S 9 /2 基态。室温组装反应生成紫色形式的化合物 2，其中红外光谱中的两个氰化物拉伸频率 (νCN 2094, 2156 cm 1 ) 表明氰化物桥接配体的部分异构。X 射线晶体结构通过检查 C 和 N 热参数证实了这种异构现象。在 40 °C 时，化合物的亚稳态绿色形式反而被分离出来，对于其中在 νCN 2156 cm 1 处的单个氰化物拉伸与未异构化的簇一致。不同外加磁场下磁化强度的温度依赖性揭示了化合物 1 中显着的轴向各向异性，具有显着的轴向零场分裂，而化合物 2 在任

  DOI：

  10.1002/zaac.200700273
• 作为产物：
  描述：

  potassium cyanide 、 [(N,N',N''-trimethyl-1,4,7-triazacyclononane)Cr(CF3SO3)3] 以 二甲基亚砜 为溶剂， 以69%的产率得到tricyano(N,N',N''-trimethyl-1,4,7-triazacyclononane-κ3N)chromium(III)
  参考文献：
  名称：

  High-Nuclearity Metal-Cyanide Clusters:  Assembly of a Cr₈Ni₆(CN)₂₄ Cage with a Face-Centered Cubic Geometry

  摘要：

  The synthesis of high-nuclearity metal-cyanide clusters presents a possible means of controlling magnetic properties in the design of new single-molecule magnets. Previous work employed tridentate blocking ligands in directing the assembly of a cubic [(tacn)(8)Co-8(CN)(12)](12+) (tacn = 1,4,7-triazacyclononane) cluster; an improved crystal structure now confirms the lack of a guest water molecule inside the cluster cage. The ability to generate larger clusters by using a blocking ligand on only one of the mononuclear reaction components is demonstrated with the synthesis of a fourteen-metal [(Me(3)tacn)(8)Cr8Ni6(CN)(24)](12+) cluster. The geometry of this cluster consists of a cube of eight Me(3)tacn-ligated Cr-III ions connected via bridging cyanide ligands to six square-planar Ni-II ions situated just above the center of each cube face. Surprisingly, no guest species are evident within the 283 Angstrom (3) cavity defined by the rigid metal-cyanide cage. Assembly of the cluster in boiling aqueous solution involves a linkage isomerization wherein the carbon end of each cyanide ligand reorients from binding a Cr-III center in the reactant to binding the softer Ni-II center in the product. Consequently, the Ni-II ions become diamagnetic, resulting in magnetic behavior at high temperatures that is consistent with eight isolated Cr-III (S = 3/2) ions per cluster. However, below 30 K, a drop in the chi T-M is attributed to weak antiferromagnetic coupling between Cr-III ions through the LUMO orbitals of the [Ni(CN)(4)](2-) like units centering each cluster face. Carrying out the assembly reaction in methanol at -40 degreesC forestalls the Linkage isomerization, yielding a high-spin green form of the cluster. Reaction of [(Me(3)tacn)(8)Cr8Ni6(CN)(24)](12+) with [Ni(CN)(4)](2-) affords an aggregate species with a tetracyanonickelate ion capping each face of the cluster through a mean Ni Ni contact of 3.00(1) Angstrom, an interaction that destroys the long-range antiferromagnetic coupling between Cr-III ions, Efforts to construct a larger cluster with an edge-bridged cubic geometry produced a linear [(Me(3-)tacn)(2)(cyclam)NiCr2(CN)(6)](2+) (cyclam = 1,4,8,11-tetraazacyclotetradecane) fragment exhibiting an S = 4 ground state. The weak ferromagnetic coupling (J = 10.9 cm(-1)) within this cluster leads to a more rapid decrease in the magnetization with increasing temperature at higher magnetic fields as a result of the Zeeman splitting and population of low-lying excited states.

  DOI：

  10.1021/ja001991j

文献信息

• Synthesis, Structure, and Magnetic Characterization of a <i>C</i>₃-Symmetric Mn^III₃Cr^III Assembly: Molecular Recognition Between a Trinuclear Mn^III Triplesalen Complex and a <i>fac</i>-Triscyano Cr^III Complex
  作者：Carl-Georg Freiherr von Richthofen、Anja Stammler、Hartmut Bögge、Marty W. DeGroot、Jeffrey R. Long、Thorsten Glaser

  DOI：10.1021/ic901148q

  日期：2009.11.2

  atoms of [(Me3tacn)Cr(CN)3]. [(talent-Bu2)(MnIII(MeOH))3}(Me3tacn)Cr(CN)3}](ClO4)3 (1) was characterized by infrared spectroscopy, elemental analysis, mass spectrometry, electron absorption spectroscopy, and magnetic measurements. The molecular structure was established for the acetate-substituted derivative [(talent-Bu2)(MnIII(MeOH))2(MnIII(OAc))}(Me3tacn)Cr(CN)3}](ClO4)2 (2) by single-crystal X-ray

  在三反应（四齿）triplesalen配位体H 6 TALEN吨-Bu 2，其中提供了三个沙仑状配位环境中的桥间亚苯基排列由间苯三酚骨架，与锰II需氧条件下的盐，得到，原位，三核Mn III三链烯复合物[（TAl t- Bu 2）Mn III（solv）n } 3 ] 3+。本种然后用发生反应[（ME 3 TACN）的Cr（CN）3 ]，以形成四核配合物[（TALEN吨-Bu 2）Mn III 3 } （Me 3 TAcn）Cr（CN）3 }] 3+（[Mn III 3 Cr III ] 3+）。在三核三链烯络合物中观察到的规则配体折叠使三个金属离子与[（Me 3 TAcn）Cr（CN）3 ]的三个面协调的氮原子反应进行了预组织。[（TALEN吨-Bu 2）（锰III（甲醇））3 } （ME 3 TACN）的Cr（CN）3 }]（CLO 4）3（1）通过红外光谱，元素分析，质谱，
• Sokol, Jennifer J.; Shores, Matthew P.; Long, Jeffrey R., Inorganic Chemistry, 2002, vol. 41, p. 3051 - 3054
  作者：Sokol, Jennifer J.、Shores, Matthew P.、Long, Jeffrey R.

  DOI：——

  日期：——
• High-Nuclearity Chromium-Nickel-Cyanide Clusters: An Open Cr8Ni5(CN)24 Cage and a C3-Symmetric Cr10Ni9(CN)42 Cluster Incorporating Three Forms of Cyanonickelate
  作者：Jennifer J. Sokol、Matthew P. Shores、Jeffrey R. Long

  DOI：10.1002/1521-3773(20010105)40:1<236::aid-anie236>3.0.co;2-c

  日期：2001.1.5