- Thermodynamics and kinetics of reaction of (Oxo)(hydroxo)molybdenumtetraphenylporphyrin with pyridine
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The reaction of meso-tetraphenylporphyrin with Mo(VI) oxide in boiling phenol resulted in a stable complex O=Mo(OH)TPP. Thermodynamics and kinetics of the reaction between (oxo)(hydroxo)molybdenumtetraphenyporphyrin with pyridine in toluene were studied by spectrophotometric method. This reaction was found to occur in three equilibrium elementary stages: replacement of OH- by Py (K 1=9.1 × 103 l/mol, k 1=5.25 s-1 mol-1 l), the formation of dication (dipyridine)(hydroxo)molybdenumtetraphenylporphyrin as a result of cleavage of a double bond Mo=O (K 2=39.3 l/mol, k 2=1.83 × 10-2 s-1 mol-1 l), and the formation of cationic complex[Mo(Py)3TPP]3+ ? 3OH- (K 3=1.0 l/mol, k 3=1.19 × 10-3 s -1 mol-1 l).
- Tipugina,Lomova,Motorina
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- Chemical composition of donor–acceptor complexes of hydroxyoxo(5,10,15,20-tetraphenylporphinato)molybdenum(V) with 3,5-dimethylpyrazole and equilibrium constants for their formation
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The results from a quantitative study of reactions between hydroxyoxo(5,10,15,20-tetraphenylporphinato)molybdenum(V) (O=Mo(OH)TPP) and 3,5-dimethylpyrazole, a biologically active base, in toluene are presented. The chemical structure and key parameters of intermediates and reaction products are determined by spectral means. The equilibrium constant (K = 51.3 L/mol) is calculated and a full kinetic description of simple reactions that occur in this system during complex transformation is obtained. The prospect of using a mixed porphyrin-containing complex as a receptor for 3,5-dimethylpyrazole, a building block for alkaloids and pharmaceutical preparations, is substantiated.
- Motorina,Lomova
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- Novel 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-2- yl)methylpyrrolidinyl[60]fullerene-hydroxyoxo(5,10,15,20-tetraphenyl-21H, 23H-porphynato) molybdenum(V) dyads
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Interaction between hydroxyoxo(5,10,15,20-tetraphenylporphyrinato) molybdenum(V) and 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′- (pyridin-2-yl)methylpyrrolidinyl[60]fullerene in toluene has been studied by means of spectrophotometry. The reaction proceeds via
- Motorina,Lomova,Troshin,Klyuev
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- Synthesis and properties of a novel porphyrin–fullerene triad assembled through donor–acceptor bonding
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Complexation of (hydroxy)(oxo)(5,10,15,20-tetraphenylporphyrinato) molybdenum(v) with 2’,5’-di(2-pyridyl)-1’- (3-pyridylmethyl) pyrrolidino[70]fullerene leading to a new donor–acceptor triad is characterized by quantitative description of the equilibrium and the reaction rate. The prospects of the triad as a photosynthetic antenna imitator and an active layer in solar energy conversion devices are substantiated.
- Motorina, Elena V.,Lomova, Tatyana N.,Klyuev, Mikhail V.
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- Quantitative study of the quasiequilibrium in the system (hydroxo)oxo-(5,10,15,20-tetraphenylporphynato)-molybdenum(V)-piperidine in toluene medium
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The quasiequilibrium interaction of (hydroxo)oxo-(5,10,15,20- tetraphenylporphynato)molybdenum(V) and piperidine in the toluene medium has been studied by means of chemical kinetics and spectrophotometric titration. It has been revealed that the molecular
- Motorina,Lomova
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- Synthesis and Structural Characterization of the Metalloporphyrin Dimer, 2, the First Product from the Reaction of Mo(CO)6 with H2TPP (tetraphenylporphyrin)
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The properties and crystal structure of 2, obtained from the reaction of Mo(CO)6 and H2TPP (tetraphenylporphyrin), are dicussed.
- Yang, Chiou-Herr,Dzugan, Sharlene J.,Goedken, Virgil L.
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- Ligand substitution equilibrium in the macrocyclic molybdenum(V) complex
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The thermodynamics of the reaction of tetraphenylporphyrin(oxo)(hydroxo) molybdenum with imidazole (Im) in toluene was studied spectrophotometrically in a polythermal mode. It was established that the reaction of Im with O=Mo(OH)TPP includes several stages, two of which can be studied by spectrophotometrical titration. The first equilibrium stage is Im coordination to the eighth coordination site (K 1 = 1.85 × 103 l/mol), the second stage is the coordination of the second Im molecule with the displacement of OH- into the outer sphere (K 2 = 4.80 × 10 2 l/mol). The enthalpy and entropy contributions to the stability constant of tetrapheny lporphyrin molybdenum(V) complexes with Im were determined. Nauka/Interperiodica 2007.
- Tipugina,Motorina,Lomova
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- Ligand substitution reactions in (dichloro)hafnium(IV) tetraphenylporphine and (oxo)(hydroxo)molybdenum(V) tetraphenylporphine
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Extra coordination and substitutions in the first coordination sphere of mixed-ligand metal porphyrins (Cl)2HfTPP and O=Mo(OH)TPP (TPP stands for the meso-tetraphenylporhine) with a molecular ligand H2S and an anionic ligand HSO4- (ligands with weak affinities to metal cations in metal porphyrins) is studied. The substitution of a hydrosulfate ion for the O2- and OH- anionic ligands in the molybdenum complex is irreversible when in concentrated aqueous H 2SO4, monohydrate, or HOAc + H2SO4 mixtures. The reaction with H2S, which is reversible in toluene, is studied by spectrophotometric titration. The stepwise substitution constants for (Cl)2HfTPP (K1 = 82 l/mol, K2 = 289 l/mol) and the one-stage SH--for-OH- substitution constant for O=Mo(OH)TPP (Ke = 83 l/mol) are determined. Both complexes are candidates for use as activators of gas-separating membranes and as components of H2S-selective sensors.
- Tipugina,Lomova
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p. 961 - 965
(2008/10/09)
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