N-methyl-tetraphenylporphyrin zinc(II) acetate | 127972-25-2

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: N-methyl-tetraphenylporphyrin zinc(II) acetate
• 英文别名: acetato(N-methyltetraphenylporphinato)zinc(II)；[(N-methyltetraphenylporphine(-1H))Zn(OAc)]；[(Ac)Zn(N-CH3)TPP]；[(AcO)Zn(N-Me)TPP]
• CAS: 127972-25-2
• 化学式: C₄₇H₃₄N₄O₂Zn
• 分子量: 752.203
• InChiKey: ISXWWSFFIKPBEI-PLILZHJESA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 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：

  N-methyl-tetraphenylporphyrin zinc(II) acetate 以 neat (no solvent, solid phase) 为溶剂， 生成 zinc tetraphenylporphyrin
  参考文献：
  名称：

  Synthesis, chemical stability, and electrocatalytic properties of zinc(II) and cobalt(II) complexes of N-methyltetraphenylporphine

  摘要：

  Distortion of flat ligand structure in metal complexes of porphyrins caused by N-methyl substitution considerably decreases the kinetic stability of these compounds in DMSO-HOAc proton-releasing medium ((AcO)Zn(N-Me)TPP (Ib) < (AcO)Co-II(N-Me)TPP (Ia) < ZnTPP (IIb) < (CoTPP)-T-II (IIa)) and their resistance to thermal destruction in crystal state {(AcO)Co-II(N-Me)TPP (Ia) < (AcO)Zn(N-Me)TPP (Ib) < H(N-Me)TPP (I) < H2TPP (II) < (CoTPP)-T-II (IIa) < ZnTPP (IIb)}, however, exerts a positive effect on the electrocatalytic activity of the compounds in the electroreduction of molecular oxygen, which changes in the following order: II < I < IIa < Ib A << Ia. It was proved by thermogravimetry and electron spectroscopy that N-substituted metal complexes with Zn(II) and Co(II), in contrast to the corresponding ligands, undergo dealkylation to form metal porphyrins (MP) when heated above 200A degrees C under both an inert and air oxygen atmosphere.

  DOI：

  10.1134/s0036023615100046
• 作为产物：
  描述：

  Cd(N-Me)TTP(OAc) 在 Zn(NO₃)2 作用下， 以 二甲基亚砜 为溶剂， 生成 N-methyl-tetraphenylporphyrin zinc(II) acetate
  参考文献：
  名称：

  Metal exchange reactions in cadmium complexes with porphyrins of various structures

  摘要：

  The reaction kinetics of the metal exchange Cd(II)-Cu(II) and Cd(II)-Zn(II) in the cadmium complexes (CdP) with porphyrin ligands (H(2)P) differing by degree of stiffness (tetraphenylporphin, N-methyltetraphenylporphin, and tetraphenyltetrabenzoporphin) in the DMSO medium, was studied using spectrophotometric method. The rate of metal exchange reaction depends on the nature of the non-planatrity of H(2)P in the structure of CdP complexes, as well as on the additional screening of the reaction center MN(4) by the extra-ligands and substituents. The reduction of the coordinating ability of the anion X(-) in the structure of the solvate-salt of incoming metal M'X(2)(Solv) (n-2) in a series: acetylacetonate > acetate > chloride > nitrate favors the metal exchange. In the most studied cases the reaction of CdP proceeds along a combined associative-dissociative mechanism. The order of the metal exchange reaction is found to be depending on temperature indicating a change in the contributions of associative and combined routes. The "pure" associative reaction mechanism in a medium of DMSO was for the first time found for the labile complex CdTPTBP with the saddle-type nonplanar ligand.

  DOI：

  10.1134/s1070363210030254

文献信息

• Some peculiarities of metal exchange reactions in porphyrin and phthalocyanine complexes
  作者：D. B. Berezin、O. V. Shukhto、M. S. Nikol?skaya、B. D. Berezin

  DOI：10.1007/s11173-005-0004-7

  日期：2005.2

  The crystal and molecular structures of the K[EuIII (Edta)(H2O)3]·3.5H2O (I) (H4Edta = ethylenediaminetetraacetic acid) and K4[Eu2III(HTtha)2] · 13.5H2O (II) (H6Ttha = triethylenetetraminehexaacetic acid) complexes have been determined by single-crystal X-ray diffraction analyses. The crystal of I belongs to orthorhombic crystal system and Fdd2 space group. The crystal data are as follows: a = 1.9849(6)nm

  K [Eu III（Edta）（H 2 O）3 ]·3.5H 2 O（I）（H 4 Edta =乙二胺四乙酸）和K 4 [Eu 2 III（HTtha）2 ]·的晶体和分子结构13.5H 2 O（II）（H 6 Ttha =三亚乙基四胺六乙酸）络合物已通过单晶X射线衍射分析确定。I的晶体属于正交晶系和Fdd2空间群。晶体数据如下：a = 1.9849（6）nm，b = 3.5598（11）nm，c = 1.2222（4）nm，V = 8.636（5）nm 3，Z = 16，M = 596.37，ρ（计算）= 1.835g / cm 3，µ = 3.166mm-1和F（000）=4752。2936年（I <2.0σ（I））反射的最终R和wR值分别为0.0269和0.0692，所有7284个唯一反射的最终R和wR值分别为0.0317和0.0708。[Eu III（Edta）（H 2 O）3 ]
• Effect of the type of molecular nonplanar structure on the chemical reactivity of NH bonds in the coordination center of porphyrin molecule
  作者：D. B. Berezin、O. V. Mal’tseva

  DOI：10.1134/s1070363209040276

  日期：2009.4

  Effect of out-of-plane screwing of the porphyrin macrocycle (H2P) by means of tetra-meso-substitution and intracyclic N-substitution on the state of NH bonds in the molecule is explored. By applying H-1 NMR, kinetic and quantum-chemical criteria of evaluation of the macrocycle NH-reactivity is found that such type of H2P screwing does not increase reactivity of the NH bonds. It is shown that increased chemical NH activity is observed only in the porphyrins undergoing at a significant conformational screwing possess the polarization of the molecular pi-system.
• ——
  作者：D. B. Berezin、N. V. Zharnikova、V. G. Andrianov、P. A. Shatunov、A. S. Semeikin

  DOI：10.1023/a:1015565132623

  日期：——

  The effect of peripheral substitution in the porphyrin macrocycle (H2OEtP, H2TPP) of the nature of the N-substituent (X = Me, Ph) and of the anion in the salt solvate (A = Ac-, NO3-, Acac(-)) on the complexation of the N-substituted porphyrins with zinc salts in DMSO is studied. The positions of the bands in the electronic absorption spectrum of the (A)M(N-X)P metal complex were found to depend only slightly on the nature of the A anion in the composition of the coordination sphere of the complex. An inhibition of coordination of the N-substituted H2TPP derivatives by zinc nitrate was discovered that is not typical of porphyrins proper. The type of hybridization of the substituted nitrogen atom in the porphyrin molecule is discussed. A mixed type of hybridization is suggested: the sp(2)- and p(3)-forms in the ligands and an almost complete transition to the p(3)-form in the N-substituted metal complexes.
• Metal exchange in cadmium porphyrins with spatially shielded coordination centers
  作者：D. B. Berezin、N. V. Lazareva、O. V. Shukhto、R. S. Kumeev、A. S. Semeikin

  DOI：10.1134/s0036023613090027

  日期：2013.9

  Shielding of coordination centers in metalloporphyrins (MPs, M = Cd) through covering it with a covalently bonded "lid" or by an endocyclic N-substituent results in retardation of metal exchange reaction (Cd/Zn or Cd/Cu) by up to 10 times. A decrease in the metal exchange rate was observed in spite of the fact that the shielding gave rise to a pronounced distortion of the predominately planar structure of aromatic ligands in the MP structure in the studied objects, which was confirmed by electronic and fluorescence spectroscopy as well as by H-1 NMR spectroscopy. It was found that 2,8,12,18-tetramethyl-3,7,13,17-tetrabutyl-10,20-di-ortho-methoxyphenylporphin exists as a mixture of cis- and trans-atropisomers with a ratio of 1: 2.
• Stability of nonplanar N-methylporphyrins and their zinc complexes
  作者：D. B. Berezin、E. N. Mis’ko、E. V. Antina、M. B. Berezin

  DOI：10.1134/s1070363206030200

  日期：2006.3

  Resistance of N-methyl-substituted porphyrins and their Zn(II) complexes to thermooxidative degradation and to the action of a DMSO-AcOH proton-donor solvent was studied by thermogravimetry and chemical kinetics. The fairly low stability of the complexes is caused by decreased planarity and, as a consequence, aromaticity of the macrorings and also by the tendency of the complexes to demethylation. The stability of the zinc complexes in AcOH varies in parallel with the degree of nonplanarity and resistance to thermooxidative degradation of their ligands.