31004-82-7Relevant articles and documents
Preparation and spectral properties of β-bromo-substituted Mn(III) tetraphenylporphyrinates
Chizhova,Zvezdina,Kataleva,Mamardashvili
, p. 1132 - 1135 (2015)
Interaction of 5,10,15,20-tetraphenylporphyrin, 2-bromo-5,10,15,20-tetraphenylporphyrin, and 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin with manganese(II) chloride in dimethylformamide has been studied by means of spectrophotometry. The corresponding chloride acido complexes of manganese(III) has been so prepared and identified. The complexes could be reduced into manganese(II) tetraphenylporphyrinates in the presence of potassium hydroxide in dimethylformamide.
Competitive Photochemical Reactions of Azidomanganese(III) Tetraphenylporphyrin in 2-Methyltetrahydrofuran
Imamura, Taira,Yamamoto, Yuichi,Suzuki, Toru,Fujimoto, Masatoshi
, p. 2185 - 2186 (1987)
The photoirradiation of MnIII(tpp)N3 (tpp = meso-tetraphenylporphinato) in the fluid solutions of 2-methyltetrahydrofuran at temperatures of 0 to -70 deg C causes competitive reactions between the oxidation of the central manganese of the compl
Molecular and ionic complexes of pyrrolidinofullerene bearing chelating 3-pyridyl units
Konarev, Dmitri V.,Khasanov, Salavat S.,Kornev, Alexey B.,Faraonov, Maxim A.,Troshin, Pavel A.,Lyubovskaya, Rimma N.
, p. 791 - 798 (2012)
Molecular and ionic complexes of cis-2′,5′-di(pyridin-3-yl) pyrrolidino[3′,4′:1,9](C60-Ih)[5,6]fullerene DP3FP with chlorobenzene (C6H5Cl), manganese(ii) tetraphenylporphyrin (MnIITPP) and tetrakis(dimethylamino)ethylene (TDAE) have been obtained for the first time. X-ray single crystal structure determination for the crystalline DP3FP·C6H5Cl (1) solvate proved unambiguously its molecular structure with the cis-arrangement of chelating 3-pyridyl groups. It has been demonstrated that DP3FP easily forms self-assembled photoactive complexes with metallated porphyrins. For example, the formation of a 1:1 complex between DP3FP and zinc (ii) tetraphenylporphyrin (ZnIITPP) in cyclohexane solution (2) was evidenced using absorption spectroscopy. A successful X-ray single crystal structure determination was performed for a self-assembled triad composed of a DP3FP molecule linked with two MnIITPP molecules in {DP3FP·(MnIITPP) 2}·(C6H4Cl2)3 (3). A strong organic donor TDAE reduces DP3FP to the radical anion state thus forming an ionic complex (TDAE+)·(DP3FP-) ·(C6H4Cl2)1.6 (4). Optical, electronic and magnetic properties of 4 were investigated in detail. The performed studies strongly suggest that pyrrolidinofullerene DP3FP can be used as a building block in the design of various organic materials with advanced optoelectronic and/or magnetic properties.
Enikolopov, N. S.,Gryaznov, V. M.,Solov'eva, A. B.,Rish, I. G.,Zavodchenko, S. I.,Ermilova, M. M.
, (1985)
Moy, Shirley A.,Bradshaw, Joseph E.,Lee, Daniel W.,Wilson, Lon J.
, p. 7 - 10 (1991)
Ionic and neutral C60 complexes with coordination assemblies of metal tetraphenylporphyrins, MIITPP2·DMP (M = Mn, Zn). Coexistence of (C60-)2 dimers bonded by one and two single bonds in the same compound
Konarev, Dmitri V.,Khasanov, Salavat S.,Saito, Gunzi,Otsuka, Akihiro,Lyubovskaya, Rimma N.
, p. 7601 - 7609 (2007)
Coordination assemblies of metal tetraphenylporphyrins, M IITPP2·DMP (M = Mn, Zn) were shown to form ionic multicomponent and neutral complexes with fullerene, {(MnIITPP) 2·DMP}·(C60-)2· (DMETEP+)2·(C6H4Cl 2)5 (1) and {(ZnTPP)2·DMP} ·(C60)2·(C6H5Cl)4 (2), where DMP = N,N′-dimethylpiperazine and DMETEP+ = the cation of N,N′-dimethyl-N′-ethylthioethylpiperazine. The crystal structure of 1 contains zigzag chains of the (Cof )2 dimers alternating with the DMETEP+ cations in the channels formed by the (MnIITPP) 2·DMP units, whereas in 2 zigzag chains of the C60 molecules are separated by the (ZnTPP)2·DMP units and C 6H5Cl molecules. The (MIITPP) 2·DMP assemblies (M = Mn, Zn) have axial M-N(DMP) bonds of 2.315(2) and 2.250(2) A length, average equatorial M-N(DMP) bonds elongated to 2.141(3) and 2.077(2) A, and MII atoms displaced from the porphyrin plane toward the ligand by 0.677 and 0.485 A, respectively. The single-bonded σ-(C60-)2 dimer coexists in 1 with the (C60-)2 dimer bonded by two single bonds with 86/14 occupancy factors. The σ-(C 60-)2 dimers are unusually stable and begin to dissociate only above a temperature of 320-330 K that results in the increase of the magnetic moment of 1 from 8.33 μB (320 K) to 8.66 μB (360 K). The electron paramagnetic resonance (EPR) signal of the dimeric phase (T 2+ centers in the (MnIITPP)2·DMP units. The dissociation of the σ-(C60-)2 dimers to the EPR-active C 60?- radical anions manifests a new broad Lorenz signal above 320 K with g = 2.0179 and ΔH = 65.5 mT. This signal can appear due to the exchange coupling between paramagnetic (MnIITPP) 2·DMP and C60?- species. The vis-NIR spectrum of the σ-(C60-)2 dimers is discussed.
Dual Reactivity of 1,2,3,4-Tetrazole: Manganese-Catalyzed Click Reaction and Denitrogenative Annulation
Chattopadhyay, Buddhadeb,Das, Sandip Kumar,Khatua, Hillol,Roy, Satyajit
supporting information, p. 304 - 312 (2020/10/29)
A general catalytic method using a Mn-porphyrin-based catalytic system is reported that enables two different reactions (click reaction and denitrogenative annulation) and affords two different classes of nitrogen heterocycles, 1,5-disubstituted 1,2,3-triazoles (with a pyridyl motif) and 1,2,4-triazolo-pyridines. Mechanistic investigations suggest that although the click reaction likely proceeds through an ionic mechanism, which is different from the traditional click reaction, the denitrogenative annulation reaction likely proceeds via an electrophilic metallonitrene intermediate rather than a metalloradical intermediate. Collectively, this method is highly efficient and offers several advantages over other methods. For example, this method excludes a multi-step synthesis of the N-heterocyclic molecules described and produces only environmentally benign N2 gas a by-product.
Efficient oxidation of cumene to cumene hydroperoxide with ambient O2 catalyzed by metalloporphyrins
Shen, Hai M.,Ye, Hong L.,Wang, Qin,Hu, Meng Y.,Liu, Lei,She, Yuan B.
, p. 314 - 322 (2021/04/09)
A novel and efficient protocol for oxidation of cumene to cumene hydroperoxide was presented using ambient O2 catalyzed by very simple metalloporphyrins. The selectivity toward cumene hydroperoxide reached 98.3% in the cumene conversion of 28.1% with T(4-COOH)PPCu as a catalyst at 80°C. The origin of the higher performance of T(4-COOH)PPCu was mainly ascribed to the low catalytic performance of copper(II) in the cumene hydroperoxide decomposition, and the ability of T(4-COOH)PP in stabilizing cumene hydroperoxide through hydrogen-bond interactions between them. Compared with current industrial processes and academic research in oxidation of cumene to cumene hydroperoxide with O2, the main superiorities of this protocol were the high selectivity, high conversion, simple catalysts, solvent-free, additive-free and mild conditions which made this work an appealing reference for the industrial oxidation of cumene to cumene hydroperoxide, as well as the oxidative functionalization of other C-H bonds in various hydrocarbons. 2021 World Scientific Publishing Company.
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.
