D. Darensbourg, J. Chojnacki, Earl V. Atnip
Jun 1, 1993
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0
Influential Citations
13
Citations
Journal
Journal of the American Chemical Society
Abstract
Cyanoacetic acid was observed to catalytically decompose to its component parts, CO 2 and CH 3 CN, in the presence of soluble tungsten(0) carboxylates. In the case in which W(CO) 5 O 2 CCH 2 CN - was used as the catalyst, the reaction was inhibited by the substrate via an equilibrium process in which the free acid displaced the carboxylate ligand and bound to the metal through the nitrogen atom. The equilibrium constant for this process was measured and determined to be 0.413 at 50 o C, where k f =6.11×10 -3 M -1 s -1 and k r =1.48×10 -2 M -1 s -1 . Activation parameters for the decarboxylation process were determined and yielded ΔH * =21.0±0.7 kcal.mol -1 and ΔS * =-3.4±1.9 eu