dichloro(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)manganese(II) | 212697-49-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: dichloro(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)manganese(II)
• 英文别名: dichloro(4,11-dimethyl-1,4,8,11-tetrazabicyclo[6.6.2]hexadecane)manganese(II)；[Mn^II(Cl)₂(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)]；Mn^II(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)Cl₂；Mn(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)Cl₂；Mn(4,11-dimethyl-1,4,8,11-teraazabicyclo[6.6.2]hexadecane)Cl₂；[Mn^II(Cl)₂(Me₂EBC)]；4,11-Dimethyl-1,4,8,11-tetrazabicyclo[6.6.2]hexadecane;manganese(2+);dichloride
• CAS: 212697-49-9
• 化学式: C₁₄H₃₀Cl₂MnN₄
• 分子量: 380.263
• InChiKey: ZXYCROYRJRYNDV-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  1.64
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  13
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dichloro(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)manganese(II) 、 重氧水 在 H₂O₂ 作用下， 以 further solvent(s) 为溶剂， 生成 di(hydroxo-(18)O)(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)manganese(IV)(2+)
  参考文献：
  名称：

  具有两个末端羟基配体的新型交叉桥联环九锰（IV）配合物的合成，表征和溶液性质。

  摘要：

  新型单体四价锰配合物，其具有桥联的Cyclam配体4,11-二甲基-1,4,8,11-四氮杂双环[6.6.2]十六烷（Me2EBC），[Mn（IV）（Me2EBC）（OH）2通过在水溶液中在NH4PF6存在下用H2O2氧化Mn（II）（Me2EBC）Cl2来合成]（PF6）2。该锰（IV）化合物的X射线晶体结构测定表明，它含有两个稀有的末端羟基配体。在乙腈中以77 K进行的EPR研究表明，在g = 1.96和3.41处有两个宽泛的共振，表明锰（IV）作为高旋转d3物种存在。该锰（IV）物种的共振拉曼光谱（rR）表明，二羟基部分Mn（IV）（OH）2也是水溶液（pH <7）中的主要物种。pH滴定提供两个pK（a）值，即6.86（4）和10.0（1），与逐步除去[Mn（IV）（Me2EBC）（OH）2]（2+）中最后两个与氧结合的质子有关。锰（IV）配合物在干乙腈中于298 K的循环伏安法表明Mn4

  DOI：

  10.1021/ic0521123
• 作为产物：
  描述：

  [MnCl₂(Py)₂] 、 4,11-dimethyl-1,4,8,11-tetraaza-bicyclo[6.6.2]hexadecane 以 乙腈 为溶剂， 生成 dichloro(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)manganese(II)
  参考文献：
  名称：

  Ultra rigid cross-bridged tetraazamacrocycles as ligands—the challenge and the solution

  摘要：

  以双碳交叉桥联四氮杂大环的质子海绵性质为代表的金属离子结合难题已经得到解决，并开发出了合成过渡金属络合物和其他金属络合物的通用方法；这些超刚性配体形成的络合物具有卓越的动力学稳定性。

  DOI：

  10.1039/a802060d
• 作为试剂：
  描述：

  3,4-二甲氧基苄醇 在 盐酸 、 dichloro(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)manganese(II) 、 双氧水 作用下， 以 水 、 乙腈 为溶剂， 反应 4.0h， 以80%的产率得到3,4-二甲氧基苯甲醛
  参考文献：
  名称：

  利用生物启发的H 2 O 2跨桥Cyclam锰配合物高效氧化苯甲酸和脂肪醇

  摘要：

  室温下，桥联的仙客来锰络合物Mn（Me 2 EBC）Cl 2有效催化苄基和脂肪醇在乙腈和水的混合物中的氧化。采用对环境无害且含氧量高的氧化剂H 2 O 2。醇转化为相应的羰基化合物的转化率达到98％，选择性好至极好。此外，在这些条件下，几种木质素模型化合物也被催化氧化，具有出色的转化率（高达96％）和选择性（高达99％）。

  DOI：

  10.1002/ejoc.201801140

文献信息

• Formation, Characterization, and O–O Bond Activation of a Peroxomanganese(III) Complex Supported by a Cross-Clamped Cyclam Ligand
  作者：Hannah E. Colmer、Anthony W. Howcroft、Timothy A. Jackson

  DOI：10.1021/acs.inorgchem.5b02398

  日期：2016.3.7

  nucleophilic reactivity of peroxomanganese(III) intermediates, as well as their conversion to high-valent oxo-bridged dimers, it remains a challenge to activate peroxomanganese(III) species for conversion to high-valent, mononuclear manganese complexes. Herein, we report the generation, characterization, and activation of a peroxomanganese(III) adduct supported by the cross-clamped, macrocyclic Me2EBC

  尽管已有报道描述过氧锰（III）中间体的亲核反应性以及它们向高价氧桥联二聚体的转化，但活化过氧锰（III）物种转化为高价单核锰仍然是一个挑战。复合体。在这里，我们报告的生成，表征和活化的过氧锰（III）加合物的交叉夹紧，大环Me 2 EBC配体（4,11-二甲基-1,4,8,11-四氮杂双环[6.6.2 ]十六烷）。已知该配体可支持具有明确光谱特性的高价单核Mn IV物种，这为从相应Mn III的O-O键活化中鉴定单核Mn IV产物提供了机会。–peroxo加合物。通过在CH中的[Mn II（Cl）2（Me 2 EBC）]中添加KO 2，在低温下制备过氧锰（III）中间体[Mn III（O 2）（Me 2 EBC）] + 2 Cl 2，该络合物的特征在于电子吸收，电子顺磁共振（EPR）和Mn K边缘X射线吸收（XAS）光谱学。[Mn III（O 2）（Me 2 EBC）] +的电子结构通过
• Topologically Constrained Manganese(III) and Iron(III) Complexes of Two Cross-Bridged Tetraazamacrocycles
  作者：Timothy J. Hubin、James M. McCormick、Nathaniel W. Alcock、Daryle H. Busch

  DOI：10.1021/ic9912225

  日期：2001.1.1

  the iron(III) complexes, while Mn3+/Mn2+ and Mn4+/Mn3+ couples were observed for the complexes with manganese(III). The manganese chemistry of 1 was studied in depth. The dichloro manganese(III) cation of 1 undergoes facile ligand substitution reactions at the labile, monodentate sites, for example substituting azide for chloride ligands. Air oxidation of the dichloro complex of Mn (1)2+ in basic solution

  4,11-二甲基-1,4,8,11-四氮杂双环[6.6.2]十六烷（1）和4,10-二甲基-1,4,7,10-四氮杂双环[5.5）的Mn3 +和Fe3 +配合物族.2]十四烷（2）是通过二价锰和铁类似物的化学氧化制备的。配体是分别衍生自cylam和cycln的乙烯交联的四氮杂大环。描述了这些配合物的合成和表征，包括X射线晶体结构的测定。结构证据表明，四齿配体在金属离子上施加扭曲的八面体几何形状，其中两个顺式位点被不稳定的配体占据。磁测量结果表明，该复合物具有典型的磁矩高自旋。循环伏安法显示，铁（III）配合物的Fe3 + / Fe2 +对可逆的氧化还原过程，锰（Ⅲ）配合物的Mn3 + / Mn2 +和Mn4 + / Mn3 +对。深入研究了1的锰化学。1的二氯锰（III）阳离子在不稳定的单齿位点进行容易的配体取代反应，例如用叠氮化物代替氯化物配体。在碱性溶液中空气氧化Mn（1）2+的二氯配
• Olefin Epoxidation by the Hydrogen Peroxide Adduct of a Novel Non-heme Mangangese(IV) Complex:  Demonstration of Oxygen Transfer by Multiple Mechanisms
  作者：Guochuan Yin、Maria Buchalova、Andrew M. Danby、Chris M. Perkins、David Kitko、John D. Carter、William M. Scheper、Daryle H. Busch

  DOI：10.1021/ic0522030

  日期：2006.4.17

  dioxygen, (18)O2, and hydrogen peroxide, H2(18)O2, confirm that an oxygen atom is transferred directly from the H2(18)O2 oxidant to the olefin substrate in the predominant pathway. The hydrogen peroxide adduct of this high-oxidation-state manganese complex, Mn(IV)(Me2EBC)(O)(OOH)+, was detected by mass spectra in aqueous solutions prepared from Mn(II)(Me2EBC)Cl2 and excess hydrogen peroxide. A Lewis acid pathway

  烯烃环氧化是一类适合于一般研究氧化过程的反应。在这里，我们报告了一种新型，交叉桥联的环酰胺锰配合物Mn（Me2EBC）Cl2（Me2EBC为4,11-二甲基-1,4,8,11-四氮杂双环[6.6.2]十六烷）对各种烯烃的催化环氧化），使用过氧化氢作为末端氧化剂，在丙酮/水（比例为4：1）中作为溶剂介质。用该系统进行的催化环氧化研究表明，反应是通过非自由基途径进行的，而不是预期的氧反弹机理，该机理是高价，后期过渡金属催化剂的特征。用新合成的[Mn（IV）（Me2EBC）（OH）2]（PF6）2（pKa = 6）直接处理烯烃。86）在中性或碱性溶液中证实了较早的观察结果，在这种情况下，氧代-Mn（IV）或氧代-Mn（V）都不负责烯烃的环氧化。在丙酮/水（H2（18）O）溶剂中使用18O标记的催化环氧化实验表明，即使在Mn（IV）之间观察到氧交换，也没有将水（H2（18）O）中的18O掺入环氧产
• New Iron(II) and Manganese(II) Complexes of Two Ultra-Rigid, Cross-Bridged Tetraazamacrocycles for Catalysis and Biomimicry
  作者：Timothy J. Hubin、James M. McCormick、Simon R. Collinson、Maria Buchalova、Christopher M. Perkins、Nathaniel W. Alcock、Pawan K. Kahol、Ahasuya Raghunathan、Daryle H. Busch

  DOI：10.1021/ja990366f

  日期：2000.3.1

  The high-spin dichloro Mn2+ and Fe2+ complexes of 4,11 dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]-hexadecane (1) and 4.10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane (2) provide durable new compounds of these elements for important fundamental studies and applications. The compounds are especially noteable for their exceptional kinetic stabilities and redox activity. The X-ray crystal structures of all four complexes demonstrate that the ligands enforce a distorted octahedral geometry on the metals with two cis sites occupied by labile chloride ligands. Magnetic measurements reveal that all are high spin with typical magnetic moments. Cyclic voltammetry of the complexes shows reversible redox processes at +0.110 and +0.038 V (versus SHE) for the Fe3+/Fe2+ couples of Fe(1)Cl-2 and Fe(2)Cl-2, respectively, while the Mn3+/Mn2+ and Mn4+/Mn3+ couples were observed at +0.585 and +1.343 V, and +0.466 and +1.232 V for the complexes Mn(1)Cl-2 and Mn(2)Cl-2, respectively. Mn2+(1) was found to react with H2O2 and other oxidizing agents to produce the Mn4+(1) complex. The catalytic efficacy of Mn4+(1) in aqueous solution has been assessed in the epoxidation reaction of carbamazepine and hydrogen abstraction reaction with 1,4-cyclohexadiene The complex has been found to be a selective catalyst, exhibiting moderate catalytic activity in oxygen transfer, but significantly more effective catalytic activity in hydrogen abstraction reactions.
• Oxo- and Hydroxomanganese(IV) Adducts: A Comparative Spectroscopic and Computational Study
  作者：Swarup Chattopadhyay、Robert A. Geiger、Guochuan Yin、Daryle H. Busch、Timothy A. Jackson

  DOI：10.1021/ic101014g

  日期：2010.8.16

  The electronic structures of the bis(hydroxo)manganese(IV) and oxohydroxomanganese(IV) complexes [Mn-IV(OH)(2)(Me2EBC)](2+) and [Mn-IV(O)(OH)(Me2EBC)](+) were probed using electronic absorption, magnetic circular dichroism (MCD), and variable-temperature, variable-field MCD spectroscopies. The d-d transitions of [Mn-IV(OH)(2)(Me2EBC))(2+) were assigned using a group theory analysis coupled with the results of time-dependent density functional theory computations. These assignments permit the development of an experimentally validated description for the pi and sigma interactions in this complex. A similar analysis performed for [Mn-IV(O)(OH)(Me2EBC)](+) reveals that there is a significant increase in the ligand character in the Mn pi* orbitals for the Mn-IV=O complex relative to the bis(hydroxo)manganese(IV) complex, whereas the compositions of the Mn sigma* orbitals are less affected, Because of the steric features of the Me2EBC ligand, we propose that H-atom transfer by these reagents proceeds via the sigma* orbitals, which, because of their similar compositions among these two compounds, leads to modest rate enhancements for the Mn-IV=O versus (MnOH)-O-IV species.