ChemInform Abstract: ALKALI-METAL-ION CATALYSIS OF THE ELECTRON-TRANSFER REACTION BETWEEN 1-PROPYL-3-CARBAMOYL-1,4-DIHYDROPYRIDINE AND HEXACYANOFERRATE(III). A LINEAR RELATIONSHIP INVOLVING CATALYTIC ACTIVITY

1981 ◽  
Vol 12 (1) ◽  
Author(s):  
T. OKAMOTO ◽  
A. OHNO ◽  
S. OKA
Keyword(s):  
Electron Transfer ◽  
Catalytic Activity ◽  
Alkali Metal ◽  
Linear Relationship ◽  
Metal Ion ◽  
Transfer Reaction ◽  
Electron Transfer Reaction ◽  
Alkali Metal Ion ◽  
Metal Ion Catalysis

Thermally Induced Electron Transfer in a CsCoFe Prussian Blue Derivative: The Specific Role of the Alkali-Metal Ion

2004 ◽  
Vol 116 (28) ◽  
pp. 3814-3817 ◽  
Author(s):  
Anne Bleuzen ◽  
Virginie Escax ◽  
Alban Ferrier ◽  
Françoise Villain ◽  
Michel Verdaguer ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Alkali Metal ◽  
Prussian Blue ◽  
Metal Ion ◽  
Specific Role ◽  
Alkali Metal Ion ◽  
Thermally Induced

Alkali metal ion catalysis in nucleophilic displacement by ethoxide ion on p-nitrophenyl phenylphosphonate: Evidence for multiple metal ion catalysis

2003 ◽  
Vol 81 (1) ◽  
pp. 53-63 ◽  
Author(s):  
Erwin Buncel ◽  
Ruby Nagelkerke ◽  
Gregory RJ Thatcher
Keyword(s):  
Alkali Metal ◽  
Transition State ◽  
Metal Ions ◽  
Metal Ion ◽  
Alkali Metal Ions ◽  
Phosphoryl Transfer ◽  
Alkali Metal Ion ◽  
Nucleophilic Displacement ◽  
Displacement Reactions ◽  
Metal Ion Catalysis

In continuation of our studies of alkali metal ion catalysis and inhibition at carbon, phosphorus, and sulfur centers, the role of alkali metal ions in nucleophilic displacement reactions of p-nitrophenyl phenylphosphonate (PNPP) has been examined. All alkali metal ions studied acted as catalysts. Alkali metal ions added as inert salts increased the rate while decreased rate resulted on M+ complexation with 18-crown-6 ether. Kinetic analysis indicated the interaction of possibly three potassium ions, four sodium ions, and five lithium ions in the transition state of the reactions of ethoxide with PNPP. Pre-association of the anionic substrate with two metals ions in the ground state gave the best fit to the experimental data of the sodium system. Thus, the study gives evidence of the role of several metal ions in nucleophilic displacement reactions of ethoxide with anionic PNPP, both in the ground state and in the transition state. Molecular modeling of the anionic transition state implies that the size of the monovalent cation and the steric requirement of the pentacoordinate transition state are the primary limitations on the number of cations that can be brought to bear to stabilize the transition state and catalyze nucleophilic substitution at phosphorus. The bearing of the present work on metal ion catalysis in enzyme systems is discussed, in particular enzymes that catalyze phosphoryl transfer, which often employ multiple metal ions. Our results, both kinetic and modeling, reveal the importance of electrostatic stabilization of the transition state for phosphoryl transfer that may be effected by multiple cations, either monovalent metal ions or amino acid residues. The more such cations can be brought into contact with the anionic transition state, the greater the catalysis observed.Key words: alkali metal ion catalysis, nucleophilic displacement at phosphorus, multiple metal ion catalysis, phosphoryl transfer.

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