31004-82-7Relevant academic research and scientific papers
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.
Aromatic olefin oxygenation with tetrahydroborate and dioxygen catalyzed by a manganese porphyrin
Shimizu,Orita,Hayakawa,Takehira
, p. 165 - 172 (1989)
Chloro(meso-tetraphenylporphyrinato)manganese(III) catalyzed the oxygenation of aromatic olefins derived from styrene with molecular oxygen in the presence of sodium tetrahydroborate in methanol at ambient temperature. Styrenes afforded mainly the Markownikov 'hydration' products, e.g. benzyl alcohols. Substitution on the olefinic carbon by the bulky group resulted in the formations of various byproducts; α-substituted styrenes afforded dimerization products, e.g. 2,2,3,3-tetraphenylbutane from 1,1-diphenylethene, and both C=C bond cleavage and α,β-diketone formation occurred in the case of β-substituted styrene, i.e. benzyl alcohol and benzil were respectively obtained from stilbene.
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.
Preparation of an Oxoporphyrinatomanganese(IV) Complex
Willner, Itamar,Otvos, John W.,Calvin, Melvin
, p. 964 - 965 (1980)
Oxo-manganese-tetraphenylporphyrin (O=MnIV-TPP) has been prepared by an oxygen-transfer reaction from iodosylbenzene to MnIITPP and characterized by its i.r. and field desorption mass spectra, which are identical to those of the prod
Synthesis of tetraphenylporphyrinate manganese(III) siloxides by silyl group transfer from silanethiols
Meininger, Daniel J.,Kasrawi, Zieph,Arman, Hadi D.,Tonzetich, Zachary J.
, p. 1970 - 1978 (2016)
Reaction of [Mn(OAc)(TPP)] (TPP = dianion of meso-tetraphenylporphine) with both HSSiiPr3 and HSSiPh3 in the presence of air leads to formation of the corresponding siloxide complexes, [Mn(OSiR3)(TPP)] (R = iPr, Ph), via silyl group transfer from S to O. The new compounds have been fully characterized in solution and the solid state and represent rare examples of Mn(III) porphyrinates containing Lewis basic axial ligands. X-ray crystallographic analyses of both complexes reveal very short Mn–O bond distances consistent with the presence of a siloxide ligand. Investigations of the reaction pathway are consistent with initial reduction of [Mn(OAc)(TPP)] to [MnII(TPP)] by the silanethiol. Subsequent aerobic oxidation of the reaction mixture is proposed to generate a Mn(III) porphyrinate and the corresponding silanol, which combine to yield the observed siloxide complex. These findings stand in sharp contrast to those of iron(III) porphyrinates, where silanethiolate complexes are stable.
Formation of Manganese(II) Porphyrin Derivatives from Manganese(III) Derivatives by Ionizing Radiation
Rao, Ramakrishna,Symons, Martyn C. R.,Harriman, Anthony
, p. 3393 - 3396 (1982)
Exposure of manganese(III) porphyrin solutions to 60Co γ-rays at 77 K gave the manganese(II) derivatives, with g (apparent) ca. 6, A(55Mn) ca. 77 G and /D/ >/= 0.3 cm-1.The spectra are very similar to those for MnII derivatives prepared chemically.Weak features in the g=2 region for these complexes were obscured by features from a symmetrical MnII derivative of unknown origin.These features grew in intensity on melting and re-freezing.These results suggest that low-temperature irradiation coupled with e.s.r. spectroscopy may be a suitable technique for detecting MnIII derivatives in biological systems.
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.
Facile Preparation of Manganese(II) Tetraphenylporphyrin by the Pyrolysis of Dimethoxomanganese(IV) Tetraphenylporphyrin
Suzuki, Toru,Imamura, Taira,Fujimoto, Masatoshi
, p. 257 - 260 (1988)
Manganese(II) tetraphenylporphyrin, MnII(tpp) (tpp=meso-tetraphenylporphinato), was afforded by the pyrolysis of MnIV(tpp)(OCH3)2 at ca 180 deg C under 10-4-10-5 Torr (1 Torr ca 133.3 Pa).The pyrolysis of Mosup
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.
