| 107222-12-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• CAS: 107222-12-8
• 化学式: C₄₈H₃₆CoN₄O₄
• 分子量: 791.831
• InChiKey: DXGBKNNVNSGNGB-NHZJRHMYSA-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：

  、 氧化亚氮 在 piperidine 作用下， 以 二氯甲烷 为溶剂， 以79%的产率得到
  参考文献：
  名称：

  含轴向结合一氧化氮的钴卟啉的合成，表征和光谱电化学。

  摘要：

  几种形式的（T（p / mX）PP）Co（NO）（p / mX = p-OCH（3）（1），p-CH（3）（2），m-CH（3）的亚硝基钴卟啉）（3），pH（4），m-OCH（3）（5），p-OCF（3）（6），p-CF（3）（7），p-CN（8））通过前驱体卟啉钴与一氧化氮的反应可以得到30-85％的收率。还通过使前体卟啉钴与四氟硼酸硝酸钠反应，然后用钴茂还原来制备化合物1-7。通过元素分析，IR和（1）H NMR光谱，质谱和UV-可见分光光度法表征了化合物1-8。它们是反磁性的，并且在1681和1695 cm（-）（1）之间的CH（2）Cl（2）中显示nu（NO）带。通过单晶X射线晶体学分析确定的1的分子结构，显示119.6（4）度的Co-NO角。1的晶体是单斜晶P2 / c，其a = 15.052（1）Å，b = 9.390（1）Å，c = 16.274（2）Å，beta = 111

  DOI：

  10.1021/ic960031o
• 作为产物：
  描述：

  3-甲氧基苯甲醛 以 丙酸 、 N,N-二甲基甲酰胺 为溶剂， 反应 26.0h， 生成
  参考文献：
  名称：

  金属卟啉与 N-羟基邻苯二甲酰亚胺的结合催化 O2 选择性无溶剂和无添加剂氧化初级苄基 C-H 键

  摘要：

  通过调整金属卟啉和 NHPI 作为二元催化剂的组合，提出了一种用 O2 无溶剂和无添加剂氧化初级苄基 C-H 键的协议，以克服当前氧化系统中遇到的缺陷。系统研究了反应温度、卟啉结构、中心金属、催化剂负载量和O2压力的影响。对于 T(2-OCH3)PPCo 和 NHPI 的优化组合，所有主要的苄基 C-H 键都可以在 120°C 和 1.0 MPa O2 下以芳香酸为主要产物有效和选择性地官能化。对于大多数在金属卟啉负载为 0.012% (mol/mol) 中具有初级苄基 C-H 键的底物，对芳香酸的选择性可高达 70-95%，转化率超过 30%。在所研究的金属卟啉中，T(2-OCH3)PPCo 的优异性能主要归因于其电荷转移效率高和中心金属 Co (II) 周围的正电荷较少，这有利于 O2 与钴 (II) 的加成形成高价金属-氧配合物，随后产生邻苯二甲酰亚胺 N-氧基自由基（PINO）并引

  DOI：

  10.1007/s10562-020-03214-y

文献信息

• Mechanism and Driving Force of NO Transfer from <i>S</i>-Nitrosothiol to Cobalt(II) Porphyrin:  A Detailed Thermodynamic and Kinetic Study
  作者：Xiao-Qing Zhu、Jian-Yu Zhang、Jin-Pei Cheng

  DOI：10.1021/ic061427v

  日期：2007.1.1

  The thermodynamics and kinetics of NO transfer from S-nitrosotriphenylmethanethiol (Ph3CSNO) to a series of alpha,beta,gamma,delta-tetraphenylporphinatocobalt(II) derivatives [T(G)PPCoII], generating the nitrosyl cobalt atom center adducts [T(G)(PPCoNO)-N-II], in benzonitrile were investigated using titration calorimetry and stopped-flow UV-vis spectrophotometry, respectively. The estimation of the energy change for each elementary step in the possible NO transfer pathways suggests that the most likely route is a concerted process of the homolytic S-NO bond dissociation and the formation of the Co-NO bond. The kinetic investigation on the NO transfer shows that the second-order rate constants at room temperature cover the range from 0.76 x 10(4) to 4.58 x 10(4) M-1 s(-1), and the reaction rate was mainly governed by activation enthalpy. Hammett-type linear free-energy analysis indicates that the NO moiety in Ph3CSNO is a Lewis acid and the T(G)PPCoII is a Lewis base; the main driving force for the NO transfer is electrostatic charge attraction rather than the spin-spin coupling interaction. The effective charge distribution on the cobalt atom in the cobalt porphyrin at the various stages, the reactant [T(G)PPCoII], the transition-state, and the product [T(G)(PPCoNO)-N-II], was estimated to show that the cobalt atom carries relative effective positive charges of 2.000 in the reactant [T(G)PPCoII], 2.350 in the transition state, and 2.503 in the product [T(G)(PPCoNO)-N-II], which indicates that the concerted NO transfer from Ph3CSNO to T(G)PPCoII with the release of the Ph3CS center dot radical was actually performed by the initial negative charge (-0.350) transfer from T(G)PPCoII to Ph3CSNO to form the transition state and was followed by homolytic S-NO bond dissociation of Ph3CSNO with a further negative charge (-0.153) transfer from T(G)PPCoII to the NO group to form the final product T(G)(PPCoNO)-N-II. It is evident that these important thermodynamic and kinetic results would be helpful in understanding the nature of the interaction between RSNO and metal porphyrins in both chemical and biochemical systems.
• Formylation of metallocomplexes of tetra-meso-(para- and meta-methoxyphenyl)porphyrins
  作者：V. D. Rumyantseva、S. V. Tsukanov、A. F. Mironov

  DOI：10.1134/s1068162007020094

  日期：2007.3

  The Vilsmeier formylation of metallocomplexes of isomeric meta- and para-methoxy-substituted tetraphenylporphyrines has was been studied. Formyl derivatives of meta-isomers were shown to form cyclization products not only in solutions, but also in the the solid state. The ability to undergo such transformations follows decreases in the trend following order: Co > Cu > Ni > Pd > Pt.