Kinetics of thermal oxidative decomposition of zinc porphyrin and phthalocyanine complexes

Lebedevа, N. Sh.; Pavlycheva, N. A.; V’yugin, A. I.

doi:10.1134/s1070363207040226

Cited by 12 publications

(7 citation statements)

References 8 publications

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“…For these MCs, the first bond that is likely to cleave is the aliphatic C–C bond in the ethyl bridge (lowest BDE); therefore, cleavage of this bond should initiate radical chain reactions. Similar observations are reported by Lebedeva et al, whose experimental results show that cracking of the substituent alkyl groups was the first stage of decomposition of zinc(II) tetra- tert -butyltetraphenylporphyrin in TGA experiments.…”

Section: Resultssupporting

confidence: 90%

Addition Reactions of Olefins to Asphaltene Model Compounds

et al. 2015

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Addition reactions have been proposed as a significant pathway for coke formation in the liquid-phase cracking of heavy oils and bitumens. In order to study the kinetics of olefin addition in the liquid phase, two alkyl-bridged aromatic compounds, with molecular weights of 899.70 g/mol and 1127.99 g/mol, were thermally cracked with 1-hexadecene, 1-octadecene, or trans-stilbene, in a batch microreactor at 375−430°C for 15 to 45 min. Reaction products were analyzed by gas chromatography, high-performance liquid chromatography, matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), and proton nuclear magnetic resonance ( 1 H NMR) spectroscopy. Kinetic data indicate a first-order reaction in model compound concentration, with energetics consistent with a free-radical chain mechanism. Tandem MS/MS and 1 H NMR spectra of the products are consistent with olefin addition through the alkyl bridge of the bridged aromatics. The results imply that (i) the addition products are able to abstract hydrogen to give detectable products faster than they decompose, and (ii) the addition products can react even more readily than the parent compounds.

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Section: Resultssupporting

confidence: 90%

Addition Reactions of Olefins to Asphaltene Model Compounds

et al. 2015

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“…Balantseva et al [28] published their findings of the thermogravimetry and thermal analysis of some porphyrinate solvates, and they mentioned that the decomposition of ZnTPP occurs at T = 463.15 K; however, no reference is included. Lebedeva et al [29] reported the decomposition of ZnTPP in air and over the temperature range of 623 K at 832 K. The temperature of decomposition was assigned as 623 K; this value is lower but consistent with that obtained by us due to the different atmosphere used. Finally, Allan and Paton [30] published the results of their thermogravimetry experiments for CoTPP, CuTPP, and ZnTPP, but in static air atmosphere, where the temperature range of the study is given, but the corresponding temperatures of decomposition are not provided.…”

Section: Thermogravimetrysupporting

confidence: 60%

Study of the stability of 5,10,15,20-tetraphenylporphine (TPP) and metalloporphyrins NiTPP, CoTPP, CuTPP, and ZnTPP by differential scanning calorimetry and thermogravimetry

Gamboa

Norzagaray-Campos

Torres

2010

The Journal of Chemical Thermodynamics

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“…Astonishingly, the monomeric Zn(II) BHPs decompose in solutions open to oxygen within 24 h. Other Zn(II) porphyrins are stable to air and moisture, , but already a simple amino substituent in the β-position of a Zn(II) porphyrin is known to lead to a similar instability . Under argon atmosphere and in solid state, the Zn(II) BHPs were stable even if exposed to light and humidity.…”

Section: Results and Discussionmentioning

confidence: 99%

Axial, Helical, and Planar Chirality in Directly Linked Basket-Handle Porphyrin Arrays

2016

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The single-electron oxidative dimerization of basket-handle porphyrins (BHPs) with different coordinated metal ions [Cu(II), Ni(II), Pd(II), Zn(II)] yielded directly meso-meso linked dimers in excellent yields. The synthetic protocol is suited for coupling substrates with different meso-substituents (H, Br, aryl, alkyl) opposite to the coupling site. Experimental findings concerning reactivities and selectivities were in good agreement with theoretical investigations using ALIE calculations. The dimers, which all are axially chiral, were resolved into their enantiomers by HPLC on a chiral phase. ECD spectra were measured in the stopped-flow mode and compared with results from quantum-chemical ECD calculations to assign the absolute configuration. One directly linked dimer was further oxidized to a fused system, which possessed a stable helical chirality. Its absolute configuration was again assigned by ECD investigations. Furthermore, functionalized BHPs and tetraarylporphyrins were coupled under Suzuki conditions to give dimers and trimers with either β-meso or β-β linkages. Because of the steric shielding of one of the BHP hemispheres, the products were formed with full diastereoselectivity regarding all porphyrin-porphyrin axes. The stereostructures of these arrays were investigated by quantum-chemical calculations (DFT-D3, TD DFT, and sTD DFT), and the absolute configurations were assigned for all chiral representatives.

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Kinetics of thermal oxidative decomposition of zinc porphyrin and phthalocyanine complexes

Cited by 12 publications

References 8 publications

Addition Reactions of Olefins to Asphaltene Model Compounds

Addition Reactions of Olefins to Asphaltene Model Compounds

Study of the stability of 5,10,15,20-tetraphenylporphine (TPP) and metalloporphyrins NiTPP, CoTPP, CuTPP, and ZnTPP by differential scanning calorimetry and thermogravimetry

Axial, Helical, and Planar Chirality in Directly Linked Basket-Handle Porphyrin Arrays

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