Mechanism of metal ion promoted hydrogen exchange reactions. Magnesium(II) and acetonyl phosphonate

1973 ◽  
Vol 95 (4) ◽  
pp. 1071-1074 ◽  
Author(s):  
Ronald. Kluger ◽  
Philip. Wasserstein
Keyword(s):  
Metal Ion ◽  
Hydrogen Exchange ◽  
Exchange Reactions

Metal ion-biomolecule interactions. Part 22.1 Cr(III)-catalyzed isotopic hydrogen exchange in methylimidazoles

2000 ◽  
Vol 78 (4) ◽  
pp. 474-486
Author(s):  
Omoshile Clement ◽  
Ikenna Onyido ◽  
Erwin Buncel
Keyword(s):  
Metal Ions ◽  
Kinetic Data ◽  
Metal Ion ◽  
Hydrogen Exchange ◽  
Careful Analysis ◽  
Order Rate Constant ◽  
Electronic Configuration ◽  
Exchange Reactions ◽  
Experimental Conditions ◽  
Isotopic Hydrogen

The detritiation kinetics of the Cr(III) complexes 1 and 3-6 have been studied in aqueous buffers at 35°C, using the liquid scintillation counting technique. Results for 5 and 6 provide benchmark kinetic data for N-T/N-H exchange under the experimental conditions of the study and have aided in the delineation of N-T/N-H from C-T/C-H exchange in the parallel reactions observed experimentally. Curved first-order plots obtained for 1, 3, and 4 were treated to yield rate constants for two parallel exchange reactions kobsA  and kobsB  for the "fast" and "slow" processes, respectively. The "fast" process has been assigned to C(2)-H exchange in 1, competing N-H and C(2)-H exchange in 3, and N-H exchange in 4. In all cases, the "slow" process is associated with C(4,5)-H exchange. Identification of exchange sites in 1, 3, and 4 was made possible by the consideration of the results of an IR spectroscopic study of hydrogen-deuterium exchange, comparison of the extent of 3H incorporatation in different complexes in the tritiation experiments, and a careful analysis of the exchange kinetic data. Analysis of the rate data indicates that Cr(III) significantly enhances C(2)-H exchange in 1 and 3, while C(4,5)-H exchange, hitherto reported in the literature only under drastic reaction conditions, was observed for 1, 3, and 4 under the mild conditions of the present study. Quantitation of the effect of Cr(III) coordination on 3H exchange in imidazole-type nuclei was achieved fully in 1; giving kM+ values of 6 × 103 and 7 × 102 M-1s-1 for C(2)-H and C(4,5)-H exchange, respectively. Using the literature value for kH+, the second-order rate constant for C(2)-H exchange under H+ catalysis, 2.9 × 102 M-1s-1, it follows that Cr(III) is ca. 20 times better as a catalyst for C(2)-H exchange in 1-methylimidazole than H+, providing the first example of a metal ion being more effective than a proton in these processes. Comparison of the results obtained with 1 with literature results for 2 shows a very large (ca. 3 × 105-fold) difference in the catalytic activities of Cr(III) and Co(III), favouring the former. The dichotomy in the effectiveness of the two metal ions in catalyzing 3H exchange in the imidazole nucleus has been ascribed to differences in (i) extent of Mn+—N bond polarization (and the consequent effect on ligand C-H acidity); (ii) electronic configuration; (iii) crystal field stabilization and activation energies; and (iv) importance of metal-ligand π back-bonding. The study highlights the diversity of factors and complexity of interactions involved in determining the role of metal ions in biological systems, especially where such processes involve complex formation between metal ions and heterocyclic fragments of biomolecules.Key words: metal ion-biomolecule interactions, methylimidazole, isotopic hydrogen exchange, catalysis by chromium.

Transalkylierung und protonenkatalysierte C-C-Spaltung bei n-Butyl-und n-Pentylbenzol in der Gasphase / Transalkylation and Proton Catalyzed C-C-Cleavage of Gaseous n-Butyl and w-Pentyl Benzenes

1979 ◽  
Vol 34 (3) ◽  
pp. 495-501 ◽  
Author(s):  
C. Wesdemiotis ◽  
H. Schwarz ◽  
C. C. Van de Sande ◽  
F. Van Gaever
Keyword(s):  
Hydrogen Exchange ◽  
Closed Shell ◽  
Open Shell ◽  
Molecular Ions ◽  
Exchange Reactions ◽  
Intramolecular Exchange ◽  
Carbon Carbon Bond ◽  
Exchange Processes ◽  
Reaction Channels ◽  
Alkyl Benzenes

Abstract The investigation of several 13carbon and deuterium labelled n-butyl and n-pentyl benzenes demonstrate that chemical ionization (reagent gas: methane) induces specific carbon-carbon bond cleavages of the alkyl group. The extent of competing reaction channels as for instance direct alkene elimination versus dealkylation/reprotonation is analyzed. Partial hydrogen exchange processes between reagent ions and substrate molecules are restricted to the phenyl ring. Intramolecular exchange reactions between the side chain and the aromatic ring which are typical for the open shell molecular ions of alkyl benzenes are not observed for analogous closed shell cations.

Catalytic deuterium exchange reactions with organics. XXIV. Electron spin resonance studies of adsorption on platinum oxide

1966 ◽  
Vol 19 (4) ◽  
pp. 529 ◽  
Author(s):  
IT Ernst ◽  
JL Garnett ◽  
WA Sollich-Baumgartner
Keyword(s):  
Transition Metal Oxides ◽  
Hydrogen Exchange ◽  
Platinum Oxide ◽  
Active Species ◽  
Paramagnetic Species ◽  
Charge Transfer Complexes ◽  
Severe Reaction ◽  
Exchange Reactions ◽  
Spin Resonance ◽  
Solid Liquid

The formation of paramagnetic species on catalyst surfaces at room temperature through the interaction of polynuclear aromatics in solid, liquid, or solute form with hydrated platinum oxide (PtO2,2H2O) is reported. The results are attributed to the formation of charge-transfer complexes, where the transferred electrons couple weakly, forming essentially a "diradicaloid" complex with a low-lying, thermally populated, triplet state. The effect of solvent, particle size, oxygen, water of crystallization, and temperature on the generation and stability of these e.s.r. active species has been investigated. The possible importance of these paramagnetic species in catalytic self-activation and hydrogen exchange reactions has been discussed. The following Group VIII transition metal oxides gave no e.s.r. spectra under relatively severe reaction conditions such as 1 hr at 120�: PdO; Ru02,2H20; RuO2; Rh2O3; IrO2,2H2O; ReO2; and NiO.

Catalytic deuterium exchange reactions with organics. XIII. Characteristic reactions of the Group VIII transition metals

1965 ◽  
Vol 18 (7) ◽  
pp. 1003 ◽  
Author(s):  
JL Garnett ◽  
WA Sollich
Keyword(s):  
Transition Metal ◽  
Hydrogen Exchange ◽  
Deuterium Oxide ◽  
Metal Catalysts ◽  
Transition Metal Catalysts ◽  
Group Viii ◽  
Exchange Reactions ◽  
Substitution Mechanism ◽  
Π Complex ◽  
Complex Adsorption

Activation procedures and hydrogen exchange reactions with six Group VIII transition metal catalysts (Pt, Pd, Ru, Rh, Ir, Ni) are reported for three characteristic reaction systems: (i) deuterium oxide/benzene, (ii) deuterium oxide/naphthalene, and (iii) deuterium oxide/n-octane. Results of these exchange reactions indicate that both π-complex adsorption and the dissociative π-complex substitution mechanism previously established for platinum are applicable to other Group VIII transition metal catalysts. For general catalytic labelling with isotopic hydrogen, platinum was found to be the most efficient of the catalysts investigated.

Tritium as a tracer in coal liquefaction. 4. Hydrogen-exchange reactions between hydrogen in coals and tritiated hydrogen molecule

1991 ◽  
Vol 5 (3) ◽  
pp. 459-463 ◽  
Author(s):  
Toshiaki Kabe ◽  
Toshiyuki Horimatsu ◽  
Atsushi Ishihara ◽  
Hideo Kameyama ◽  
Kyoko Yamamoto
Keyword(s):  
Hydrogen Molecule ◽  
Hydrogen Exchange ◽  
Coal Liquefaction ◽  
Exchange Reactions
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