32195-55-4Relevant academic research and scientific papers
Magnetocaloric effect and heat capacity of high-spin manganese complexes in a disperse state
Korolev,Aref'Ev,Lomova,Klyueva,Zakharov,Korolev
, p. 1631 - 1635 (2010)
Magnetothermal properties of high-spin chloro(2,3,7,8,12,13,17,18- octaethylporphyrinato)manganese(III), chloro(5,10,15,20-tetraphenylporphyrinato) manganese(III), bromo(5,10,15,20-tetraphenylporphyrinato)manganese(III), and (acetato)(5,10,15,20-tetraphenylporphyrinato)manganese(III) complexes as 6% water suspensions were determined by the microcalorimetric method at 298 K in a magnetic field of 0-1.0 T. It was established that when the magnetic field was applied, the temperature of the systems increases, leading to positive values of the magnetocaloric effect: the higher the magnetic field induction, the higher the values. It is shown that the dependences of the heat capacity of the complexes' solid particles on the magnetic field induction are of an extreme nature with a heat capacity in the area above 0.6 T less than that in the zero field. The regularities of the dynamics of the numerical values of the change in enthalpy and magnetic entropy of the manganese complexes when a growing magnetic field was applied and the regularities of the influence of the acidoligand in pentacoordinated complexes on their magnetothermal properties were considered.
A manganese porphyrin-α-cyclodextrin conjugate as an artificial enzyme for the catalytic epoxidation of polybutadiene
Zhang, Qi-Wei,Elemans, Johannes A. A. W.,White, Paul B.,Nolte, Roeland J. M.
, p. 5586 - 5589 (2018)
We describe a manganese porphyrin-α-cyclodextrin conjugate as a catalyst for the epoxidation of cis-polybutadiene with trans-epoxide preference, which is a reverse stereoselectivity as compared to normal porphyrin catalysts. A clamp-like mechanism is prop
Hydrogen-bonded chain structure of a six-coordinate 5,10,15,20-tetraphenylporphinatomanganese(III) complex
Hill, Jonathan P.,Santiago, Julio,Sugino, Takushi,Shiro, Motoo,Shimizu, Yo
, p. 107 - 111 (2001)
In methanolic solutions, disproportionation of the TCNQ anion radical to neutral TCNQ0 and the dianion TCNQ2- followed by aerobic oxidation of TCNQ2- results in the formation of methyl-4-dicyanomethylene benzoate anion (MDCB-). This anion coordinates to the manganese(III) atom of 5,10,15,20-tetraphenylporphinatomanganese(III) leading to the complex whose X-ray crystal structure is reported. The crystal had the monoclinic space group P21/n with unit cell dimensions a = 13.327(3), b = 20.236(6), c = 16.914(5) ? and β = 92.26(2)°. An important driving force behind the crystal packing is a hydrogen bonding interaction between non-identical ligands of adjacent molecules.
A rare μ-hydroxo-bridged species. Synthesis, structure, and properties of μ-hydroxo(tetraphenylporphyrinatomanganese(III))(phthalocyaninato-(azido) chromium(III)), [(TPP)Mn-O(H)-CrPc(N3)]
Donzello, Maria Pia,Bartolino, Laura,Ercolani, Claudio,Rizzoli, Corrado
, p. 6988 - 6995 (2006)
A novel ditetrapyrrolic, heteroleptic, and heterometallic (Mn-Cr) μ-hydroxo-bridged complex has been prepared, and its structural and general properties have been studied. The species μ-hydroxo(tetraphenylporphyrin- atomanganese(III))(phthalocyaninato(azido)chromium(III)), [(TPP)Mn-O(H)- CrPc(N3)], isolated as a chloronaphthalene (CINP) solvate, has been structurally characterized by single-crystal X-ray work. The two (TPP)Mn and CrPc(N3) fragments are held together by the bridging μ-hydroxo ion with long Mn-O [1.993(5) A] and Cr-O [1.976(5) A] bond distances and a Mn-O(H)-Cr angle of 163.7(3)°. The five-coordinate Mn center in the (TPP)Mn fragment is displaced from the TPP rigorously planar central N 4 core by 0.128 A, and the environment is typical of a Mn III high-spin site. The six-coordinate CrIII in the CrPc(N3) moiety lies practically in the plane of the phthalocyanine macrocycle (displacement toward the azido group: 0.054 A). The average Mn-Npyr and Cr-Npyr bond distances are 2.011(6) and 1.982(6) A, respectively, and the Mn-Cr bond distance is 3.929(2) A. The porphyrin and phthalocyanine rings are in an almost eclipsed position [5.16(2)°], and the mean planes of the two macrocycles form a dihedral angle of 5.79(4)°. Crystal data for [(TPP)Mn-O(H)-CrPc(N3)] ·2CINP, C76H45CrMnN15O·2C 10H7Cl: a = 16.645(3) A, b = 17.692(4) A, c = 25.828(5) A, α = 90°, β= 98.79(3)°, γ= 90°, space group P21/c (No. 14), V = 7517(3) A3, Z= 4, R1 = 0.086, and wR2 = 0.267. IR-and UV-vis-near-IR spectral and room temperature magnetic susceptibility data of the [Mn-Cr] species are also presented.
Cycloaddition reaction of propylene oxide and carbon dioxide over NaX zeolite supported metalloporphyrin catalysts
Zhang, Fengyong,Xie, Yujia,Liu, Pingle,Hao, Fang,Yao, Zhengjie,Luo, He'An
, p. 1894 - 1899 (2014)
Metalloporphyrin catalysts has attracted extensive attention as the result of their outstanding biomimetic catalytic properties. In this paper, different kinds of unsupported (Co(TPP), MnIII(TPP)Cl and CoIII(TPP)Cl) and NaX zeolite supported metalloporphy
Nitrene Photochemistry of Manganese N-Haloamides**
Bhuvanesh, Nattamai,Das, Anuvab,Figgins, Matthew T.,Hicks, Madeline H.,Ozarowski, Andrew,Powers, David C.,Reid, Kaleb A.,Telser, Joshua,Van Trieste, Gerard P.
supporting information, p. 26647 - 26655 (2021/11/18)
Manganese complexes supported by macrocyclic tetrapyrrole ligands represent an important platform for nitrene transfer catalysis and have been applied to both C?H amination and olefin aziridination catalysis. The reactivity of the transient high-valent Mn nitrenoids that mediate these processes renders characterization of these species challenging. Here we report the synthesis and nitrene transfer photochemistry of a family of MnIII N-haloamide complexes. The S=2 N-haloamide complexes are characterized by 1H NMR, UV-vis, IR, high-frequency and -field EPR (HFEPR) spectroscopies, and single-crystal X-ray diffraction. Photolysis of these complexes results in the formal transfer of a nitrene equivalent to both C?H bonds, such as the α-C?H bonds of tetrahydrofuran, and olefinic substrates, such as styrene, to afford aminated and aziridinated products, respectively. Low-temperature spectroscopy and analysis of kinetic isotope effects for C?H amination indicate halogen-dependent photoreactivity: Photolysis of N-chloroamides proceeds via initial cleavage of the Mn?N bond to generate MnII and amidyl radical intermediates; in contrast, photolysis of N-iodoamides proceeds via N?I cleavage to generate a MnIV nitrenoid (i.e., {MnNR}7 species). These results establish N-haloamide ligands as viable precursors in the photosynthesis of metal nitrenes and highlight the power of ligand design to provide access to reactive intermediates in group-transfer catalysis.
Linkage Isomers of 4-Methylimidazolate Mn(II) Porphyrinates: Hindered or Unhindered?
Zhao, Jianping,Qian, Fei,Guo, Wenping,Li, Jianfeng,Lin, Zeyuan
, p. 7465 - 7474 (2021/05/26)
Three different manganese(II) porphyrins have been exploited to react with 4-methylimidazolate (4-MeIm-), and the five-coordinate products are characterized by ultraviolet-visible, single-crystal X-ray, and electronic paramagnetic resonance spectroscopies. Interestingly, 4-MeIm- is found to bond to the metal center through either of the two N atoms (N1 or N3), which yielded two linkage isomers with either an unhindered or a hindered ligand conformation, respectively. Investigations revealed it is the large metal out-of-plane displacements (Δ24 and Δ4 ≥ 0.59 ?) that have rendered the equivalence of two isomers with a small energy difference (5.2-8.3 kJ/mol). The nonbonded intra- and intermolecular interactions thus become crucial factors in the balance of linkage isomerization. All of the products in both solution and solid states show the same characteristic resonances of high-spin Mn(II) (S = 5/2) with g⊥ ≈ 5.9 and g⊥ ≈ 2.0 at 4 K, consistent with the weak effects of the axial ligand on core conformation and metal electronic configurations. Zero-field splitting parameters obtained through simulations are also reported.
Method for synthesizing tetraaryl manganese porphyrin through synchronous aldehyde and pyrrole condensation and bivalent manganese salt oxidation insertion reaction
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Paragraph 0028-0029, (2020/09/08)
The invention discloses a method for synthesizing tetraaryl manganese porphyrin by synchronous aldehyde and pyrrole condensation and bivalent manganese salt oxidation insertion reaction. Aromatic aldehyde, pyrrole and manganese dichloride are refluxed in
Surface molecular engineering of axial-exchanged Fe(III)Cl- and Mn(III)Cl-porphyrins towards enhanced electrocatalytic ORRs and OERs
Attatsi, Isaac Kwaku,Zhu, Weihua,Liang, Xu
supporting information, (2020/03/23)
Herein, pyrene-pyridine (Pyr-Py) molecule was applied as the axial exchanged ligand to bridge Fe(III) and Mn(III)porphyrin immobilized on rGO. These axially exchanged metalloporphyrin functionalized nanocomposites revealed enhanced electrochemically catal
Crystallographic identification of a series of manganese porphyrin complexes with nitrogenous bases
Lahanas, Nicole,Kucheryavy, Pavel,Lalancette, Roger A.,Lockard, Jenny V.
, p. 304 - 312 (2019/02/20)
Studying the axial ligation behavior of metalloporphyrins with nitrogenous bases helps to better understand not only the biological function of heme-based protein systems, but also the catalytic properties of porphyrin-based reaction sites in other biomim
