trans-[CrF2(py)4]ClO4 | 27731-45-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-[CrF2(py)4]ClO4
• 英文别名: trans-[Cr(pyridine)4F2]ClO4；trans-[Cr(py)4F2][ClO4]
• CAS: 27731-45-9
• 化学式: C₂₀H₂₀CrF₂N₄*ClO₄
• 分子量: 505.849
• InChiKey: UCPDHKGEWNORDP-UHFFFAOYSA-K

计算性质

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

反应信息

• 作为反应物：
  描述：

  trans-[CrF2(py)4]ClO4 、 N,N'-bis((3,5-di-tert-butyl)-2-hydroxybenzyl)-1,2-diaminoethane 以 乙二醇甲醚 为溶剂， 以52%的产率得到
  参考文献：
  名称：

  Synthesis, Crystal Structure, and Magnetic Properties of a Ferromagnetically Coupled Difluoro-Bridged Dinuclear Chromium(III) Complex with a Substituted Tetrahydrosalen Derivative as Ligand

  摘要：

  A novel difluoro-bridged dinuclear chromium(III) complex has been synthesized by the reaction of trans-[Cr-(py)(4)F-2]ClO4 in 2-methoxyethanol with a substituted tetrahydrosalen derivative L(8) (L(8) means the negatively charged ligand obtained by dissociation of two protons from H(2)L(8) = N,N'-bis(2-hydroxy-3,5-di-tert-butylbenzyl)-1,2-ethanediamine), The crystal structure of [CrL(8)F](2) . 2C(3)H(8)O(2) has been determined. The crystal system is triclinic, and the lattice constants are a 9.604(2) Angstrom, b = 13.346(2) Angstrom, c 15.751(2) Angstrom, alpha = 74.00(1)degrees, beta = 87.94(1)degrees, and gamma = 70.55(1)degrees. Z = 1 and the volume of the unit cell is 1826.40(49) Angstrom(3). The space group is <(P)over bar 1> (No. 2). The refinement of 456 variables includes 6279 of the 7631 independent reflections, The final residual is 4.08%. The centrosymmetric dinuclear molecule consists of two slightly distorted octahedrally cis coordinated chromium centers bound together by two fluoride bridges. The Cr-F-Cr angle is 100.90(4)degrees, and the Cr-F(bridge) distances are 2.0172(8) and 1.9754(9) Angstrom, and the Cr-Cr distance is 3.0787(4) Angstrom. The configuration of the dinuclear molecule is cis, cis-O, O'-Delta, Lambda, where cis refers to the position of the two oxygen donors and Delta and Lambda refer to the configuration of the two N, O chelates of the tetradentate ligand L(8) at each of the two chromium(III) centers. The two chromium-(III) centers in the complex are ferromagnetically coupled. On basis of measurements of the field-dependent magnetization and the magnetic susceptibility, respectively, it has been shown unambiguously that the ground state is a septet state. It has not been possible to determine the monoatomic zero field splitting parameter D from the magnetic susceptibility measurements, but the parameter has been determined from the EPR spectra measured at 4 and 21 K. From simulation of the EPR spectra the following parameters have been obtained: J = -1.4 cm(-1), D-e = 0.008 cm(-1), E(e) = -0.015 cm(-1), D-a = D-b = -0.658 cm(-1), E(a) = E(b) = 0.133 cm(-1), g(xa) = g(xb) = g(ya) = g(yb) = 1.98 and g(za) = g(zb) = 2.00.

  DOI：

  10.1021/ic960342z
• 作为产物：
  描述：

  potassium perchlorate 、 difluorotetrapyridinechromium(III) nitrate 以 水 为溶剂， 生成 trans-[CrF2(py)4]ClO4
  参考文献：
  名称：

  Costachescu, N., Annales Scientifiques de l'Universite de Jassy, 1914, vol. 8, p. 16 - 23

  摘要：

  DOI：

文献信息

• Preparation of μ-Cyano Dinuclear Chromium(III) Complexes M^I[F(en or tn)₂Cr(NC)Cr(CN)₅] from the Doubly Complexed Salts of the Form M^I[CrF(H₂O)(en or tn)₂][Cr(Cn)₆]
  作者：Makoto Johda、Masatatsu Suzuki、Akira Uehara

  DOI：10.1246/bcsj.62.738

  日期：1989.3

  Preparation of the μ-cyano dinuclear complexes MI[F(en or tn)2Cr(NC)Cr(CN)5]·nH2O from the double complexes MI[CrF(H2O)(en or tn)2][Cr(CN)6]·nH2O was carried out both in the solid state and in solution, where MI is Li+, Na+, K+, or Rb+ ion; en and tn stand for 1,2-ethanediamine and 1,3-propanediamine, respectively. The desired μ-cyano dinuclear complexes were successfully obtained in solution, but

  从双配合物 MI[CrF(H2O)(en or tn)2][Cr(CN)5]·n 制备 μ-氰基双核配合物 MI[F(en or tn)2Cr(NC)Cr(CN)5]·n 6]·n 在固态和溶液中均进行，其中 MI 是 Li+、Na+、K+ 或 Rb+ 离子；en 和 tn 分别代表 1,2-乙二胺和 1,3-丙二胺。在溶液中成功获得了所需的 μ-氰基双核复合物，但双核和三核复合物的混合物与未知的固态聚合物物质一起形成。由于自旋禁止跃迁（4A2g→2Eg），双核配合物的电子光谱显示出小而清晰的带。双核配合物的磁矩在环境温度下为 3.4-3.5 μβ，在 80 K 下为 2.2-2.4 μβ，远小于自旋值（3.87 BM）。
• Kinetic studies using Co(III) and Cr(III) complexes of 1,4,7,11-tetraazaundecane (2,2,3-tet) and the crystal structure of trans-[CrCl2(2,2,3-tetH)(OH2)]Cl·ClO4
  作者：Donald A. House、Janne Svensson

  DOI：10.1016/s0020-1693(97)06170-7

  日期：1998.8

  of loss of the first chloro ligand from trans-(R,S)(S,R)-[MCl2(2,2,3-tet)]+ (Mo = Co, Cr) to give trans-(R,S)(S,R)-[MCl(2,2,3-tet)(OH2)]2+ has been measured spectrophotometrically. Kinetic parameters (25.0°C) are: M = Co (0.01 M HCl)kH = 2.03 × 10−3 s−1, ΔH≠ = 102±4 kJ mol−1, ΔS≠ = +45±8 J K−1 mol−1; M = Cr (0.1 M HNO3)kH = 7.66 × 10−6 s−1, ΔH≠ = 99.0±2, ΔS≠ = −11±4. For Co(III), the loss of the second

  摘要反式-（R，S）（S，R）-[MCl2（2,2,3-tet）] +（Mo = Co，Cr）生成反式-（R ，S）（S，R）-[MCl（2,2,3-tet）（OH2）] 2+已通过分光光度法进行了测量。动力学参数（25.0°C）为：M = Co（0.01 M HCl）kH = 2.03×10-3 s-1，ΔH≠= 102±4 kJ mol-1，ΔS≠= + 45±8 JK-1 mol -1; M = Cr（0.1 M HNO3）kH = 7.66×10-6 s-1，ΔH≠= 99.0±2，ΔS≠= -11±4。对于Co（III），第二个氯配体（kH2的损失伴随着kH2（0.01 M HCl; 25.0°C）= 8.78×10-5 s-1，ΔH≠= 100的反式→顺式-β异构化， ΔS≠= +14而对于Cr（III），第二步由于CN键断裂而复杂，开环复合物反式[[CrCl2（2,2,3-tetH）（OH2）]
• Structural and spectroscopic properties of trans-difluoro(1,4,8,12-tetraazacyclopentadecane)chromium(III) perchlorate hydrate
  作者：Jong-Ha Choi、In-Gyung Oh、Keon Sang Ryoo、Woo-Taik Lim、Yu Chul Park、Mohammad Hossein Habibi

  DOI：10.1016/j.saa.2006.02.006

  日期：2006.12

  of X-ray crystallography. The resolved band maxima of the electronic d-d spectrum are fitted with secular determinant for quartet state energy of d(3) configuration in tetragonal field including configurational but neglecting spin-orbit coupling. It is confirmed that the fluoride has strong sigma- and pi-donor properties toward the chromium(III) ion and the nitrogen atoms of the [15]aneN(4) ligand also

  已确定[CrF（2）（[15] aneN（4））] ClO（4）.H（2）O（[15] aneN（4）= 1,4,8,12-四氮杂环十五烷）的结构通过在173 K上进行的单晶X射线衍射研究。该复合物在三元晶系的空间群P1-中结晶，该空间群具有两个单核分子式单元，其尺寸为a = 9.6117（7）A，b = 10.2882（7） ）A，c = 11.0001（7）A和alpha = 99.7570（10）度，beta = 105.6080（10）度和gamma = 113.7130（10）度。络合阳离子单元的中心Cr原子呈八面体配位，四个氮原子和两个氟原子处于反式位置。[15] aneN（4）配体的三个六元和一个五元螯合环是在椅子扭转（歪斜）-椅子-gauche构象序列。gauche五元环与相反的扭曲六元环杂乱无章。手性N原子中的四个H原子具有反式II（CTCg）型构型。平均Cr-N和Cr-F键分别为2
• Synthesis, crystal structure and spectroscopic properties of trans-difluoro(1,4,7,11-tetraazaundecane)chromium(III) perchlorate
  作者：Jong-Ha Choi、Dohyun Moon

  DOI：10.1016/j.molstruc.2013.12.008

  日期：2014.2

  Abstract The structure of trans-[Cr(2,2,3-tet)F2]ClO4 (2,2,3-tet = 1,4,7,11-tetraazaundecane) has been determined by single-crystal X-ray diffraction. The complex crystallizes in the space group P 1 ‾ of the triclinic system with two mononuclear formula units in a cell of dimensions a = 5.6741(11), b = 9.971(2), c = 13.222(3) A, α = 73.76(3)o, β = 81.08(3)° and γ = 85.12(3)°. The chromium(III) atom is

  摘要 反式-[Cr(2,2,3-tet)F2]ClO4 (2,2,3-tet = 1,4,7,11-四氮杂十一烷)的结构已通过单晶 X 射线衍射确定. 配合物在三斜晶系的空间群 P 1 ‾ 中结晶，在尺寸 a = 5.6741(11), b = 9.971(2), c = 13.222(3) A, α = 73.76( 3)o, β = 81.08(3)° 和 γ = 85.12(3)°。铬 (III) 原子处于略微扭曲的八面体环境中，由 2,2,3-tet 的四个 N 原子和两个 F 配体在相互反式（meso RS）几何结构中协调。平均 Cr-N(2,2,3-tet) 和 Cr F 键长分别为 2.064(9) 和 1.885(7) A。晶体堆积由几个氢键稳定。已经测量了 5 K 尖线吸收光谱和 298 K FT 红外和紫外可见光谱。使用电子跃迁，已进行配体场优化以确定配位原子的金属-配
• Effects of steric constraint on chromium(III) complexes of tetraazamacrocycles, 4: Comparison of the trans-difluoro-complexes of tet a, 1,4-C2-cyclam, and 1,11-C3-cyclam
  作者：Michael T. Vagnini、W. Caleb Rutledge、Chuanjiang Hu、Donald G. VanDerveer、Paul S. Wagenknecht

  DOI：10.1016/j.ica.2006.08.037

  日期：2007.4

  The synthesis and characterization of the trans-difluorochromium(III) complexes of the constrained macrocyclic ligands 1,4-C-2-cyclam = 1,4,8,1 1-tetraazabicyclo[10.2.2]hexadecane and 1,11-C-3-cyclam = 1,4,8,11-tetraazabicyclo[9.3.3]heptadecane is reported. Only trans complexes are formed, and the structures of both trans-[Cr(1,4-C-2-cyclam)F-2]ClO4 and trans-[Cr(1,11-C-3-cyclam)F-2]CIO4 are presented. The photochemical and photophysical behavior of the 1,4-C-2-cyclam and 1, 11-C-3-cyclam complexes is compared with that of the corresponding tet a (C-meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) complex. The constraint imposed by the additional bridging groups of 1,4-C-2-cyclam and 1, 11-C-3-cyclam distorts the complexes away from both octahedral symmetry and centrosymmetry, as evidenced by the bond angles that deviate from ideal 90 degrees and 180 degrees values and by a significant distortion of the Cr(N-4) plane. This reduction in symmetry correlates with a monotonic increase in the extinction coefficients in going from the tet a to the 1, 11-C-3-cyclam, to the 1,4-C-2-cyclam complex. These three complexes also exhibit large variations in their aqueous room-temperature excited state behavior; namely, the lifetimes of the T-2(1g) (Oh) excited states are 30,60, and 1.0 mu s for the tet a, 1,11-C-3-cyclam, and 1,4-C-2-cyclam complexes, respectively. Studies of the excited-state lifetime of these complexes in acidified H2O/dimethyl sulfoxide over the temperature range between -30 and +95 degrees C suggest that the 1,4-C-2-cyclarn complex accesses a temperature-dependent relaxation mechanism at significantly lower temperatures than do the tet a or 1, 11-C-3-cyclam complexes. The emission behavior of these complexes is also solvent-dependent, consistent with established theories that the degree of splitting of the emitting T-2(1g) (Oh) state varies with the hydroxylic nature of the solvent. (c) 2006 Elsevier B.V. All rights reserved.