Energy Barriers for Alkaline Hydrolysis of Carboxylic Acid Esters in Aqueous Solution by Reaction Field Calculations

2000 ◽  
Vol 104 (32) ◽  
pp. 7672-7678 ◽  
Author(s):  
Chang-Guo Zhan ◽  
Donald W. Landry ◽  
Rick L. Ornstein
Keyword(s):  
Aqueous Solution ◽  
Carboxylic Acid ◽  
Alkaline Hydrolysis ◽  
Energy Barriers ◽  
Reaction Field ◽  
Hydrolysis Of ◽  
Acid Esters

scholarly journals Hydrolysis of Carboxylic Acid Esters of Thiocholine and its Analogues. 2. Alkaline Hydrolysis.

1958 ◽  
Vol 12 ◽  
pp. 1492-1506 ◽  
Author(s):  
Edith Heilbronn ◽  
William Taub ◽  
David Ginsburg ◽  
K. Hartiala ◽  
S. Veige ◽  
...  
Keyword(s):  
Carboxylic Acid ◽  
Alkaline Hydrolysis ◽  
Hydrolysis Of ◽  
Acid Esters

The Chemical Evolution of a Nitrogenase Model, 20 Alkyl Molybdates(VI) and the Mechanism of Hydrocarbon Production by Nitrogenase [1]

1982 ◽  
Vol 37 (3) ◽  
pp. 380-385 ◽  
Author(s):  
G. N. Schrauzer ◽  
Laura A. Hughes ◽  
Norman Strampach
Keyword(s):  
Aqueous Solution ◽  
Alkaline Hydrolysis ◽  
Room Temperature ◽  
Bond Cleavage ◽  
Model Compounds ◽  
Hydrocarbon Production ◽  
Acidic Solutions ◽  
Reducing Conditions ◽  
Hydrolysis Of ◽  
Derivatives Of

Abstract Colorless alkylmolybdates(VI) of composition R-MoO3-are generated in aqueous solutions by the alkaline hydrolysis of complexes R-Mo(Bpy)(0)2Br(Bpy = 2,2′-bipyridyl, R = CH3 and higher alkyl). At room temperature in alkaline aqueous solution, the new organometallic derivatives of oxomolybdate(VI) are remarkably resistant against Mo-C bond hydrolysis. Decomposition occurs more rapidly on heating, affording unrearranged alkanes according to the eq.: R-MoO3- + OH-→RH + Mo04=. In acidic solutions, the methylmolybdate(VI) species decomposes with the formation of a mixture of methane and ethane while higher alkylmolybdates carrying hydrogen in the β-position relative to molybdenum undergo Mo-C bond heterolysis by way of β-elimina-tion: R-CH2CH2-MoO3 → Mo+4 (aq) + H+ + R-CH = CH2. The Mo-C bond of alkylmolybdates is resistant to oxidants but is very sensitive to cleavage under reducing conditions. Reductive Mo-C bond cleavage occurs particularly rapidly in the presence of thiols and reduced ferredoxin model compounds. The latter reactions simulate the terminal steps of hydrocarbon producing reactions of nitrogenase with alternate substrates such as CN-, R-CN or R-NC, confirming previous mechanistic conclusions concerning the mechanism of nitrogenase action.

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