Hydrogen exchange studies. 17. Base-catalyzed isotopic exchange of molecular hydrogen. 5. The potassium anilide-aniline system

1987 ◽  
Vol 91 (14) ◽  
pp. 3879-3883 ◽  
Author(s):  
E. Buncel ◽  
B. C. Menon
Keyword(s):  
Molecular Hydrogen ◽  
Hydrogen Exchange ◽  
Isotopic Exchange

Theory of Hydrogen Interactions with Amorphous Silicon

1999 ◽  
Vol 557 ◽  
Author(s):  
Chris G. Van De Walle ◽  
Blair Tuttle
Keyword(s):  
Amorphous Silicon ◽  
First Principles ◽  
Molecular Hydrogen ◽  
Hydrogen Exchange ◽  
Defect Formation ◽  
Exchange Process ◽  
Current Understanding ◽  
First Principles Calculations ◽  
Microscopic Mechanism ◽  
Enhanced Stability

AbstractWe present an overview of recent results for hydrogen interactions with amorphous silicon (a-Si), based on first- principles calculations. We review the current understanding regarding molecular hydrogen, and show that H2 molecules are far less inert than previously assumed. We then discuss results for motion of hydrogen through the material, as relating to diffusion and defect formation. We present a microscopic mechanism for hydrogen-hydrogen exchange, and examine the metastable ≠ SiH2 complex formed during the exchange process. We also discuss the enhanced stability of Si-D compared to Si-H bonds, which may provide a means of suppressing light-induced defect generation.

Metal ion – biomolecule interactions. Part 16. C(2)-H isotopic exchange in Co(III)-coordinated imidazoles

1995 ◽  
Vol 73 (6) ◽  
pp. 772-780 ◽  
Author(s):  
Erwin Buncel ◽  
Fan Yang ◽  
Robert Y. Moir ◽  
Ikenna Onyido
Keyword(s):  
Metal Ions ◽  
Metal Ion ◽  
Hydrogen Exchange ◽  
Isotopic Exchange ◽  
Negative Charge ◽  
Ligand Complex ◽  
Transition State Stabilization ◽  
Anionic Species ◽  
Metal Ligand ◽  
Ligand Bond

Transition-metal-bound imidazoles are suitable models for evaluating the roles of metal ions in biomolecules having the imidazole moiety and similar heterocyclic residues as part of their structure. Such studies provide useful insights into metal–biomolecule interactions in biological systems, especially when the lability of the metal–ligand bond is substantially reduced, such that the identity of the metal–ligand complex is preserved during the course of the reaction under investigation. The present paper reports on a kinetic study of tritium exchange from the C(2) position of the imidazole moiety in the substitution-inert complex cations [Co(NH3)5[2-3H]-imidazole]3+ (1) and [Co(NH3)5-1-methyl-[2-3H]-imidazole]3+ (2). Rate–pH profiles have been determined in aqueous solution at 60 °C. Both substrates are believed to react through rate-determining attack of hydroxide ion (kM+ pathway) at C(2)-T. Dissection of the kinetic data reveals an additional pathway for 1 consequent upon deprotonation of its pyrrole-like N-H(T) to yield 3, which is then attacked by hydroxide at C(2) (kM pathway). The ratio kM+/kM = 103 that is obtained is in accord with the expected reduced reactivity of 3. Comparison of the present data with those reported for a variety of heterocyclic substrates shows that the order of reactivity, protonated [Formula: see text] metal ion coordinated [Formula: see text] neutral form of substrates, prevails. The superiority of the proton over metal ions in catalyzing isotopic hydrogen exchange is attributed to its larger ground state acidifying effect coupled with the greater transition state stabilization it affords, relative to metal ions. The exchange reaction of 3 via the kM pathway is the first example of a reactive anionic species in which the negative charge is located α to the exchanging C-H. Keywords: tritium exchange, cobalt (III)-coordinated imidazoles.

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