[Cr(cyclam)(OTf)₂]OTf | 362054-73-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: [Cr(cyclam)(OTf)₂]OTf
• CAS: 362054-73-7
• 化学式: CF₃O₃S*C₁₂H₂₄CrF₆N₄O₆S₂
• 分子量: 699.535
• InChiKey: NFUSBMSKUPNHFP-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：

  [Cr(cyclam)(OTf)₂]OTf 在 lithium diisopropylamide 作用下， 以 四氢呋喃 、 氯苯 、 乙腈 为溶剂， 生成 Cr(1,4,8,11-tetraazacyclotetradecane)(4-ethynyl-5-methyl-4',5'-ethylenedithiotetrathiofulvalene)2BF4(acetonitrile)(PhCl)2
  参考文献：
  名称：

  Weak Ferromagnetism and Strong Spin−Spin Interaction Mediated by the Mixed-Valence Ethynyltetrathiafulvalene-Type Ligand

  摘要：

  A new chromium complex with ethynyltetrathiafulvalene (TTF)-type ligands, [CrCyclam(C C-5-methyl-4'5'-ethylenedithio-TTF)(2)]OTf ([1]OTf), was synthesized. The cyclic voltammetry of the complex shows two reversible oxidation waves owing to the first and second oxidation of the TTF unit. The electrochemical oxidation of [1]OTf in a Bu4NClO4 or Bu4NBF4 solution of a 1:1 acetonitrile-chlorobenzene mixture gave isostructural crystals of [1][ClO4](2)(PhCl)(2)(MeCN) and [1] [BF4](2)(PhCl)(2)(MeCN), where two mixed-valence TTF units of adjacent complexes form a dinner radical cation. The crystal structures are characterized bi an alternating chain of S = 3/2 Cr(3+)Cyclam units and S = 1/2 (TTF)(2)(+) dimers. These two paramagnetic components are connected directly by an ethynyl group, resulting in a strong intrachain spin-spin interaction of 2J/k(B) = -30 and -28 K for [ClO4](-) and [BF4](-) salts, respectively (H = 2J Sigma S-i(i)center dot Si+1). Both salts show a weak ferromagnetic transition at 23 K thanks to interchain antiferromagnetic interaction between TTF dimers. The remanent magnetizations and coercive forces of nonoriented samples at 1.8 K are 0.016 mu(B) and 90 mT for the [ClO4](-) salt and 0.010 mu(B) and 50 mT Oe for the [BF4](-) salt, respectively. The weak ferromagnetism is attributed to the Dzyaloshinsky-Moriya interaction between adjacent TTF dimers and/or the single-ion anisotropy of [1](2+).

  DOI：

  10.1021/ic102384s
• 作为产物：
  描述：

  6,6'-bi(1,4,8,11-tetra-azacyclotetradecane) 以 二甲基亚砜 为溶剂， 生成 [Cr(cyclam)(OTf)₂]OTf
  参考文献：
  名称：

  Cr（III）双环素二聚体的光物理观察

  摘要：

  摘要制备了单核环素（[14] aneN 4）X 2和双核双环素（[14] aneN 4）2 X 4的铬（III）配合物，并对其光物理性质进行了研究。在这些饱和的大环系统中，检查了含X =氯，溴和硫氰酸根络合物的酸胺顺式单体和顺式，顺式二聚体对的光物理表现。UV-vis吸收和发射在二聚体光谱中显示出与溴和硫氰酸根络合物的单体母体相对的异常特征，这与基于电荷转移介导的交换过程所预测的一致；然而，这些分子的激发态性质表现出相反的行为，因此不可能基于交换机制来解释所观察到的行为。

  DOI：

  10.1016/s0020-1693(01)00323-1

文献信息

• Synthesis of trans bis-alkynyl complexes of Co(III) supported by a tetradentate macrocyclic amine: A spectroscopic, structural, and electrochemical analysis of π-interactions and electronic communication in the CCMCC structural unit
  作者：Parth U. Thakker、Roberto G. Aru、Chivin Sun、William T. Pennington、Adam M. Siegfried、Elyse C. Marder、Paul S. Wagenknecht

  DOI：10.1016/j.ica.2013.11.036

  日期：2014.2

  Alkynyl complexes of the type trans-[Co(cyclam)(CCR)2]OTf have been prepared and characterized by UV–Vis spectroscopy, 1H NMR, vibrational spectroscopy (infrared and Raman), and cyclic voltammetry. Where appropriate the data is compared to the corresponding Cr(III) and Rh(III) complexes. Though the arylalkynyl ligands have been shown to act as π-donors for the corresponding Cr(III) complexes, vibrational

  已经制备了反式-[Co（cyclam）（CCR）2 ] OTf类型的炔基配合物，并通过UV-Vis光谱，1 H NMR，振动光谱（红外和拉曼光谱）和循环伏安法进行了表征。在适当的情况下，将数据与相应的Cr（III）和Rh（III）配合物进行比较。尽管已表明芳基炔基配体充当相应Cr（III）配合物的π供体，但振动光谱表明，芳基炔基配体与Co（III）之间的π相互作用非常弱，并且吸电子性更高的三氟丙炔基配体可能表现为对Co（III）的弱π受体。反式-[Co（cyclam）（CCCF 3）2的X射线晶体结构还报道了] OTf和反式-[Cr（cyclam）（CCCF 3）2 ] OTf，并且对MC和CC键长的分析与对三氟丙炔基配体的这种理解是一致的。反式-[Co（cyclam）（CCR）2 ] OTf配合物的循环伏安法表明，当R = C 6 H 5或p -C 6 H 4 CH 3时，Co III /
• Synthesis of cis and trans Bis-alkynyl Complexes of Cr(III) and Rh(III) Supported by a Tetradentate Macrocyclic Amine: A Spectroscopic Investigation of the M(III)–Alkynyl Interaction
  作者：Chivin Sun、Christopher R. Turlington、W. Walsh Thomas、James H. Wade、Wade M. Stout、David L. Grisenti、William P. Forrest、Donald G. VanDerveer、Paul S. Wagenknecht

  DOI：10.1021/ic2009336

  日期：2011.10.3

  than for the analogous Rh(III) complexes, a result that can be interpreted in terms of the alkynyl ligands acting as π-donors. UV–vis spectra of the Cr(III) and Rh(III) complexes are dominated by strong charge transfer (CT) transitions. In the case of the Rh(III) complexes, these CT transitions obscure the metal centered (MC) transitions, but in the case of the Cr(III) complexes the MC transitions are

  [M（cyclam）（CCR）2 ] OTf类型的炔基配合物（其中cyclam = 1,4,8,11-四氮杂十四烷； M = Rh（III）或Cr（III）； R =苯基，4-甲基苯基（4-三氟甲基苯基，4-氟苯基，1-萘基，9-菲基和环己基）的制备方法为一锅法合成，其中将2当量的RCCH和4当量的BuLi加入到在THF中合适的[M（cyclam）（OTf）2 ] OTf络合物。使用溶解度差异分离炔基配合物的顺式和反式异构体，并使用红外光谱法对CH 2摇摆和NH弯曲区域进行立体化学表征。所有的反式-[M（cyclam）（CCR）2]光学传递函数显示出复合物2071和2109厘米之间的强拉曼频带-1，归因于ν小号（C≡C）。Cr（III）配合物的拉伸频率比类似的Rh（III）配合物低21–28 cm –1，这一结果可以用炔基配体作为π供体来解释。Cr（III）和Rh（III）配合物的紫外可见
• Kinetics and mechanism of carboxylate complex formation of macrocyclic chromium(III) complexes
  作者：J. Eriksen、L. Mønsted、O. Mønsted

  DOI：10.1016/s0020-1693(02)00996-9

  日期：2002.9

  unusually large formation constant for the monoacetato complex, about 105M−1 at 25 °C, which makes acetate a better ligand for the macrocyclic chromium(III) complex than for the proton. The kinetic behaviour of the acetatoaqua- and the diacetato-complex is markedly different. This is rationalized in terms of the differences in basicity of the two complexes, resulting from the differences in intra-molecular

  大环rac -5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷配体与乙酸/乙酸盐之间的顺式铬（III）配合物平衡的动力学和热力学已在1 M（H / Na）（OH / Br）的温度范围和从强酸性溶液到强碱性溶液的酸性范围内进行了研究。该系统的特征在于单乙酰基配合物的形成常数非常大，约为10 5 M -1在25°C的条件下，这使乙酸盐成为大环铬（III）络合物比质子更好的配体。乙酰水合双乙酸酯配合物的动力学行为明显不同。这是由于分子内氢键模式的差异而导致的两种络合物碱度的差异而合理化的，这使未质子化的乙酰水合络合物和双乙酸根的质子化形式变得稳定。
• Emissive Chromium(III) Complexes with Substituted Arylethynyl Ligands
  作者：David L. Grisenti、W. Walsh Thomas、Christopher R. Turlington、Matthew D. Newsom、Christopher J. Priedemann、Donald G. VanDerveer、Paul S. Wagenknecht

  DOI：10.1021/ic801376p

  日期：2008.12.15

  Arylethynylchromium(III) complexes of the form trans-[Cr(cyclam)(CCC(6)H(4)R)(2)]OTf (where cyclam = 1,4,8,11-tetraazacyclotetradecane, R = H, CH(3), or CF(3) in the para position, and OTf = trifluoromethanesulfonate) have been prepared and characterized by IR spectroscopy and X-ray diffraction. The complexes are emissive with excited-state lifetimes in a deoxygenated fluid solution between 200 and

  反式-[Cr（cyclam）（CCC（6）H（4）R）（2）] OTf（其中cyclam = 1,4,8,11-四氮杂环十四烷，R = H，CH （3），或对位CF（3），且OTf =三氟甲磺酸盐）已制备并通过红外光谱和X射线衍射进行了表征。在200至300微米之间的脱氧流体溶液中，配合物以激发态寿命发射。
• Trifluoropropynyl as a Surrogate for the Cyano Ligand and Intense, Room-Temperature, Metal-Centered Emission from Its Rh(III) Complex
  作者：Chivin Sun、Parth U. Thakker、Levan Khulordava、Daniel J. Tobben、Seth M. Greenstein、David L. Grisenti、Andrew G. Kantor、Paul S. Wagenknecht

  DOI：10.1021/ic3016113

  日期：2012.10.15

  spectra for all three bear a remarkable similarity to that of the trans-M(cyclam)(CN)2+ cations. The trifluoropropynyl complex of Co3+ shows electrochemical behavior nearly identical with that of its dicyano analogue. Metal-centered phosphorescence from the Rh(III) complex in room-temperature aqueous solution has a quantum yield of 0.12 and a lifetime of 73 μs, nearly 10 times higher than those of its dicyano

  所述配体trifluoropropynyl-C≡CCF 3进行了研究作为一个可能的替代物为氰基配体。该类型的复合物的反式- [M（cyclam）（C≡CCF 3）2 ]光学传递函数（其中M =铬3+，钴3+，和Rh 3+ ;光学传递函数=三氟甲磺酸酯）来制备，然后，其特征在于电子光谱和通过循环伏安法测定Co 3+络合物。这三个光谱的紫外可见光谱与反式-M（cyclam）（CN）2 +阳离子具有显着的相似性。Co 3+的三氟丙炔基络合物显示出与其二氰基类似物几乎相同的电化学行为。Rh（III）络合物在室温水溶液中以金属为中心的磷光的量子产率为0.12，寿命为73μs，几乎是其二氰基类似物的10倍。