Kinetics and mechanism of the reaction of chelated Pd(ii) complexes with thiols in acidic aqueous solution. Synthesis and crystal structure of [Pd(bpma)Cl]Cl·H2O (bpma = bis(2-pyridylmethyl)amine)

2002 ◽  
pp. 951 ◽  
Author(s):  
Živadin D. Bugarčić ◽  
Günter Liehr ◽  
Rudi van Eldik
Keyword(s):  
Crystal Structure ◽  
Aqueous Solution ◽  
Kinetics And Mechanism ◽  
Solution Synthesis ◽  
Acidic Aqueous Solution ◽  
Synthesis And Crystal Structure ◽  
Mechanism Of The Reaction

Kinetics and mechanism of the reaction of iron(III) with 6-methyl-2,4-heptanedione and 3,5-heptanedione

1990 ◽  
Vol 55 (8) ◽  
pp. 1984-1990 ◽  
Author(s):  
José M. Hernando ◽  
Olimpio Montero ◽  
Carlos Blanco
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Activation Parameters ◽  
Enol Form ◽  
Kinetics And Mechanism ◽  
Kinetic Constants ◽  
Steric Factors ◽  
Kinetics Of ◽  
Mechanism Of The Reaction

The kinetics of the reactions of iron(III) with 6-methyl-2,4-heptanedione and 3,5-heptanedione to form the corresponding monocomplexes have been studied spectrophotometrically in the range 5 °C to 16 °C at I 25 mol l-1 in aqueous solution. In the proposed mechanism for the two complexes, the enol form reacts with the metal ion by parallel acid-independent and inverse-acid paths. The kinetic constants for both pathways have been calculated at five temperatures. Activation parameters have also been calculated. The results are consistent with an associative activation for Fe(H2O)63+ and dissociative activation for Fe(H2O)5(OH)2+. The differences in the results for the complexes of heptanediones studied are interpreted in terms of steric factors.

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