[FeCl(1,4,8,11-tetraazacyclotetradecane-1-acetic acid monoanion)](PF6) | 315188-64-8

• 英文名称: [FeCl(1,4,8,11-tetraazacyclotetradecane-1-acetic acid monoanion)](PF6)
• 英文别名: [(cyclamacetate)FeCl]PF6
• CAS: 315188-64-8
• 化学式: C₁₂H₂₅ClFeN₄O₂*F₆P
• 分子量: 493.62
• InChiKey: MCYGTGNQWVBDBS-UHFFFAOYSA-L

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：

  [FeCl(1,4,8,11-tetraazacyclotetradecane-1-acetic acid monoanion)](PF6) 、 四丁基氯化铵 以 丙酮 为溶剂， 以90%的产率得到dichloroiron(1+);2-(1,4,8,11-tetrazacyclotetradec-1-yl)acetate
  参考文献：
  名称：

  Reactivity of a novel Fe(III) carboxymethylenecyclam complex towards dioxygen and superoxide

  摘要：

  The synthesis and physico-chemical characterization of a novel Fe(III) low-spin (V/Delta = 0.648), macroyclic complex, [Fe(III)L-(Cl-)]Cl having the pentadentate ligand N-carboxymethylene-1,4,8,11-tetraazacyclotetradecane, AcOH[14]aneN(4), is reported. It has been shown that the complex undergoes a reversible one-electron reduction (E(1/2)= -0.19 +/- 0.01 V versus NHE in DMSO/Bu(4)NBF(4) solution) forming the Fe(II) complex which reacts rapidly with dioxygen, if present. Under aerobic conditions, the electrochemical response of [Fe(III)L(Cl-)](+) indicates the production of an Fe(III) mu-peroxo dimer. On the basis of stopped-flow kinetics analysis in aqueous solution, it has been demonstrated that the Fe(III) complex accelerates dismutation of the superoxide radical, k = 3.0 +/- 1.0 x 10(7) M(-1) s(-1); 21.0 degrees C; pH = 8.1. Moreover, ESR studies on potassium superoxide in DMSO show that the radical is rapidly removed by [Fe(III)L(Cl-)](+). In the course of this reaction, a new ferric low-spin form of the Fe(III) complex with lower g anisotropy (V/Delta = 0.332; g(x) = 2331, g(y) = 2.192, g(z) = 1.989) has been found.

  DOI：

  10.1016/0020-1693(95)04463-j
• 作为产物：
  描述：

  iron(II) chloride tetrahydrate 、 在 air 作用下， 以 甲醇 为溶剂， 以46%的产率得到[FeCl(1,4,8,11-tetraazacyclotetradecane-1-acetic acid monoanion)](PF6)
  参考文献：
  名称：

  Reactivity of a novel Fe(III) carboxymethylenecyclam complex towards dioxygen and superoxide

  摘要：

  The synthesis and physico-chemical characterization of a novel Fe(III) low-spin (V/Delta = 0.648), macroyclic complex, [Fe(III)L-(Cl-)]Cl having the pentadentate ligand N-carboxymethylene-1,4,8,11-tetraazacyclotetradecane, AcOH[14]aneN(4), is reported. It has been shown that the complex undergoes a reversible one-electron reduction (E(1/2)= -0.19 +/- 0.01 V versus NHE in DMSO/Bu(4)NBF(4) solution) forming the Fe(II) complex which reacts rapidly with dioxygen, if present. Under aerobic conditions, the electrochemical response of [Fe(III)L(Cl-)](+) indicates the production of an Fe(III) mu-peroxo dimer. On the basis of stopped-flow kinetics analysis in aqueous solution, it has been demonstrated that the Fe(III) complex accelerates dismutation of the superoxide radical, k = 3.0 +/- 1.0 x 10(7) M(-1) s(-1); 21.0 degrees C; pH = 8.1. Moreover, ESR studies on potassium superoxide in DMSO show that the radical is rapidly removed by [Fe(III)L(Cl-)](+). In the course of this reaction, a new ferric low-spin form of the Fe(III) complex with lower g anisotropy (V/Delta = 0.332; g(x) = 2331, g(y) = 2.192, g(z) = 1.989) has been found.

  DOI：

  10.1016/0020-1693(95)04463-j

文献信息

• Structural, Spectroscopic, and Computational Study of an Octahedral, Non-Heme {Fe−NO}^6-8 Series:  [Fe(NO)(cyclam-ac)]^2+/+/0
  作者：Ricardo García Serres、Craig A. Grapperhaus、Eberhard Bothe、Eckhard Bill、Thomas Weyhermüller、Frank Neese、Karl Wieghardt

  DOI：10.1021/ja030645+

  日期：2004.4.28

  complexes structures, energetics, IR parameters, and Mössbauer parameters as well as EPR parameters (g-values and hyperfine couplings) have been calculated using state-of-the art DFT methods which are compared to experiment. The results establish unequivocally that 3 is indeed the elusive [FeNO]8 species. Furthermore a detailed picture of the bonding in the low-spin non-heme iron nitrosyl series [FeNO]6,

  低自旋 [FeIICl(cyclam-ac)] 与 CH3CN 中的 NO 反应生成八面体非血红素（亚硝基）铁络合物 [Fe(NO)(cyclam-ac)](PF6) (2)，S = 1/2，可被（三（4-溴苯基）铵基）六氯锑酸盐单电子氧化成复合物 [Fe(NO)(cyclam-ac)](PF6)2 (1')，S = 0，或络合物 [Fe(NO)(cyclam-ac)]Cl(ClO4).H2O (1); (cyclam-ac)- 代表 1,4,8,11-四氮杂环十四烷-1-乙酸的五齿单阴离子。同理，在CH3CN溶液2中可以通过一个电子电化学或化学还原成中性络合物[Fe(NO)(cyclam-ac)]0(3)，S=0。1-3代表[FeNO]的成员分别为6-8系列。这三种物质的电子结构已通过 EPR、UV-vis、Mössbauer 和 IR 光谱进行光谱阐明。1 和 2 的晶体结构已通过 X
• Mononuclear (Nitrido)iron(V) and (Oxo)iron(IV) Complexes via Photolysis of [(cyclam-acetato)Fe^III(N₃)]⁺ and Ozonolysis of [(cyclam-acetato)Fe^III(O₃SCF₃)]⁺ in Water/Acetone Mixtures
  作者：Craig A. Grapperhaus、Bernd Mienert、Eckhard Bill、Thomas Weyhermüller、Karl Wieghardt

  DOI：10.1021/ic0005238

  日期：2000.11.13

  azide derivative has been determined as the tetraphenylborate salt (2b). Reaction of 1 with silver triflate yields [(cyclam-acetato)Fe(O3SCF3)]PF6 (3), which partially dissociates triflate in nondried solvents to yield a mixture of triflate and aqua bound species. Each of the iron(III) derivatives is low-spin (d5, S = 1/2) as determined by variable-temperature magnetic susceptibility measurements, Mössbauer

  加入KPF6后，单阴离子，五配位配体1,4,8,11-四氮杂十四烷-1-乙酸锂Li（环酰胺乙酸酯）与FeCl3反应生成[[（cyclam-acetato）FeCl] PF6（1）为红色微晶固体。在加入KPF 6之前加入过量的NaN 3产生叠氮化物衍生物[（环素-乙酰基）FeN 3] PF 6（2a），为橙色微晶。叠氮化物衍生物的X射线晶体结构已经确定为四苯基硼酸盐（2b）。1与三氟甲磺酸银反应生成[（环素-乙酰基）Fe（O3SCF3）] PF6（3），该三氟甲磺酸酯在非干燥溶剂中部分解离三氟甲磺酸盐，生成三氟甲磺酸盐和水结合物种的混合物。每个铁（III）衍生物都是低自旋的（d5，S = 1/2），这是通过可变温度磁化率测量，Mössbauer和EPR光谱确定的。低自旋铁（II）（d6，S = 0）1red和2ared配合物已通过电化学和化学方法制备，并已通过Mössbauer光谱进行了表征。冷冻乙腈中419
• Effect of N-Methylation of Macrocyclic Amine Ligands on the Spin State of Iron(III):  A Tale of Two Fluoro Complexes
  作者：John F. Berry、Eckhard Bill、Ricardo García-Serres、Frank Neese、Thomas Weyhermüller、Karl Wieghardt

  DOI：10.1021/ic051823y

  日期：2006.3.1

  [(trimethylcyclamacetate)FeF]PF6 (3) are presented. Compound 1 is prepared in good yields from the analogous chloro complex, whereas 3 is prepared by hydrolysis of the oxo-bridged diiron compound (Me3cyclam-acetate)Fe-O-FeCl3 (2) in the presence of PF(6) anions. Magnetic susceptibility and spectroscopic data including electron paramagnetic resonance and Mossbauer spectra indicate that 1 contains low-spin Fe(III)

  介绍了[（环乙酸氨基酯）FeF] PF6（1）和相应的N-甲基化[[（环甲基乙酸氨基酯）FeF] PF6（3）的合成和表征。化合物1是由类似的氯配合物高收率制备的，而化合物3是在PF（6）阴离子存在下通过羰基桥联二铁化合物（Me3cyclam-acetate）Fe-O-FeCl3（2）的水解而制备的。磁化率和包括电子顺磁共振和莫斯鲍尔光谱的光谱数据表明，1包含低自旋的Fe（III）（S = 1/2），而3包含高自旋（S = 5/2）。通过密度泛函理论对两种八面体氟络合物进行了理论研究，以确定两个分子的自旋态为何不同。无论是否包含溶剂化模型，使用B3LYP函数计算的能量都可以正确地预测1为低旋转S = 1/2基态，而3为高旋转。1和3之间的差异很可能是由N-甲基引起的空间效应的组合，这些效应会迫使Fe-N键距比通常的3长，并且还会引起电子效应，这会导致N -甲基化的配体比其非甲基化的配体更弱的σ供体。