trans-diaqua(1,4,8,11-tetraazacyclotetradecane)chromium(III) | 287097-24-9

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: trans-diaqua(1,4,8,11-tetraazacyclotetradecane)chromium(III)
• 英文别名: trans-Cr(1,4,8,11-tetraza-cyclotetradecane)(H2O)2(3+)；trans-diaqua(cyclam)chromium(III)
• CAS: 287097-24-9；85281-22-7；93219-78-4；99572-59-5
• 化学式: C₁₀H₂₈CrN₄O₂
• 分子量: 288.354
• InChiKey: MAESKPFEJJKWIZ-UHFFFAOYSA-N

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-diaqua(1,4,8,11-tetraazacyclotetradecane)chromium(III) 在 HClO₄ 作用下， 以 水 为溶剂， 生成
  参考文献：
  名称：

  Nair, Balachandran Unni; Ramasami; Ramaswamy, Inorganic Chemistry, 1986, vol. 25, # 1, p. 51 - 55

  摘要：

  DOI：
• 作为产物：
  描述：

  cis-{Cr(1,4,8,11-tetraazacyclotetradecane)(NH3)2}(3+) 在 水 作用下， 以 水 为溶剂， 生成 trans-diaqua(1,4,8,11-tetraazacyclotetradecane)chromium(III)
  参考文献：
  名称：

  激发态三环仙客来配合物的电子转移和能量转移猝灭以及铬（II）产物的氧化还原反应

  摘要：

  The 2E excited states trans-[*Cr([14]aneN4)(NH3)2]3+ and trans-[*Cr([14]aneN4)(CN)2]+ oxidize methyl viologen radical cation, MV+, in D2O with rate constants k = 1.09 x 10(9) M-1 s-1 and 3.10 x 10(9) M-1 s-1, respectively, at 298 K and 0.050 M ionic strength. The initial chromium(II) products rapidly aquate to yield trans-[Cr([14]aneN4)(H2O)2]2+, which reduces MV2+ back to MV+. This reaction is strongly catalyzed by coordinating anions Cl-, Br-, and SCN-. For X = Cl and Br, the final chromium product is trans-Cr([14]aneN4)(H2O)(X)]2+. The kinetics obey a mixed third-order rate law, k(obs) = k(x)[MV2+] [trans-Cr-([14]aneN4)(H2O)22+][X-1, with k(Cl) = 4.65 x 10(5) M-2 s-1 and k(Br) = 5.22 x 10(5) M-2 s-1 at 298 K and 0.25 M ionic strength. The SCN--catalyzed reaction has a more complex rate law and yields trans-[Cr([14]aneN4)-(NCS)2]+ (NCS)2]+ as the chromium product implying trans-[Cr([14]aneN4)(NCS)2] as the sole kinetically important form of chromium(II). The quenching of trans-[*Cr([14]aneN4)(CN)2]+ by Cr(H2O)62+ (k = 5.23 x 10(7) M-1 s-1), V(H2O)62+ (k = 2.08 X 10(7)), and VO(H2O)52+ (k = 4.54 X 10(6)) takes place by energy transfer.

  DOI：

  10.1021/j100149a026

文献信息

• Electron-Transfer Reactions of Nitrosyl and Superoxo Metal Complexes
  作者：Wenjing Song、Arkady Ellern、Andreja Bakac

  DOI：10.1021/ic800867j

  日期：2008.9.15

  nitrosyl complexes L(H2O)CrNO(2+) (L = L(1) = 1,4,8,11-tetraazacyclotetradecane, L(2) = meso-Me 6-1,4,8,11-tetraazacyclotetradecane) are oxidized by Ru(bpy)3(3+) to LCr(H2O)2(3+) and NO with rate constants k = 2.22 M(-1) s(-1) (L(1)) and 6.83 (L(2)). Analogous reactions of the superoxo complexes L(H2O)CrOO(2+) are only slightly faster, k = 45 M(-1) s(-1) (L(1)) and 15 M(-1) s(-1) (L(2)). A related rhodium

  新型亚硝基铬络合物L（H2O）CrNO（2+）（L = L（1）= 1,4,8,11-四氮杂十四烷，L（2）= meso-Me 6-1,4,8,11-四氮杂十四烷）被Ru（bpy）3（3+）氧化为LCr（ ）2（3+）和NO，速率常数k = 2.22 M（-1）s（-1）（L（1））和6.83（ L（2））。超氧配合物L（ ）CrOO（2+）的类似反应仅稍快一点，k = 45 M（-1）s（-1）（L（1））和15 M（-1）s（-1 ）（L（2））。相关的铑配合物L（2）（ ）RhOO（2+）具有k = 15.8 M（-1）s（-1）。这些结果，结合我们对Cr（aq）NO（2+）和Cr（aq）OO（2+）进行氧化的较早数据，表明热力学在确定氧化动力学中仅发挥了适度的作用。这种现象在氢化铑和氢过氧化物配合物的氧化中更为明显，
• Electron paramagnetic resonance and UV–Vis absorption study of trans-(1,4,8,11-tetraazacyclotetradecane)chromium(III) complexes
  作者：Shoji Ueki、Jun Yamauchi

  DOI：10.1016/s0020-1693(02)00899-x

  日期：2002.10

  quartet excited states of these complexes were assigned on the basis of a Gaussian analysis of UV–Vis absorption spectra. The spin Hamiltonian parameters of the ground states, especially the zero-field splittings, were determined from the randomly oriented frozen solution electron paramagnetic resonance spectra. The calculated zero-field splitting parameters determined from the second-order spin–orbit

  该电子结构的反式- [CR III（cyclam）X 2 ] Ñ +（cyclam = 1,4,8,11-四氮杂，X =氯-，OH - ，和H 2O）进行了调查。这些配合物的自旋四重态激发态是根据高斯分析的UV-Vis吸收光谱确定的。基态的自旋哈密顿参数，特别是零场分裂，是从随机取向的冻结溶液电子顺磁共振光谱中确定的。由与最接近的激发四重态的二阶自旋轨道耦合确定的计算出的零场分裂参数被发现与实验观察到的相偏离。发现该偏差反映了轴向结扎剂的结合价。
• Direct Kinetic Studies of Atom Transfer and Electron Transfer Reactions of Hydroperoxo and High-Valent Oxo Complexes of Chromium
  作者：Oleg Pestovsky、Andreja Bakac

  DOI：10.1021/ja0382213

  日期：2003.12.1

  A macrocyclic hydroperoxo chromium complex reacts with triphenyl phosphine in an acid-catalyzed oxygen-atom transfer reaction, k = 850 M-2 s-1. In a competing process, the hydroperoxo complex is converted to a dioxo chromium(V) species, which reacts with PPh3 by electron transfer, k = 4.4 x 105 M-1 s-1.

  大环氢过氧铬配合物在酸催化的氧原子转移反应中与三苯基膦反应，k = 850 M-2 s-1。在竞争过程中，氢过氧化物络合物转化为二氧铬 (V) 物质，通过电子转移与 PPh3 反应，k = 4.4 x 105 M-1 s-1。
• Generation of a macrocyclic Cr(V) complex and its reactivity toward organic and inorganic reductants and DNA
  作者：Andreja Bakac、Wei-Dong Wang

  DOI：10.1016/s0020-1693(99)00255-8

  日期：2000.1

  The complex (LCr)-Cr-1(H2O)(2)(2+) (L-1 = 1,4,8,11-tetraazacyclotetradecane) reacts with molecular oxygen to yield an end-on superoxo complex, L-1(H2O)CrOO2+, with a rate constant k(on) = (1.80 +/- 0.06) x 10(8) M-1 s(-1) in acidic aqueous solutions. The reduction of L-1(H2O)CrOO2+ with one-electron reductants generates a transient species, believed to be (LCrOOH2+)-Cr-1 which undergoes a first-order transformation to an oxochromium(V) complex, (LCrO3+)-Cr-1, k = 0.19 s(-1) in 0.02 M HClO4. The ion (LCrO3+)-Cr-1 reacts rapidly with a number of inorganic and organic reductants, H2O2, and DNA. The extent and nature of the DNA damage depend on the reductant used to generate (LCrO3+)-Cr-1, suggesting that different reductants have different scavenging abilities toward the intermediates responsible for DNA damage. In the absence of oxidizable substrates, (LCrO3+)-Cr-1 decays in a first-order process, k = 0.39 +/- 0.05 s-(1). (C) 2000 Elsevier Science S.A. All rights reserved.
• Bakac, Andreja; Scott, Susannah L.; Espenson, James H., Journal of the American Chemical Society, 1995, vol. 117, # 24, p. 6483 - 6488
  作者：Bakac, Andreja、Scott, Susannah L.、Espenson, James H.、Rodgers, Kenton R.

  DOI：——

  日期：——