ChemInform Abstract: SYNTHESIS AND BASE HYDROLYSIS KINETICS OF (CO((15)ANEN5)DMF)3+. THE ACCELERATED HYDROLYSIS OF AN O-COORDINATED AMIDE AND BASE HYDROLYSIS OF THE RESULTING FORMATO COMPLEX

1982 ◽  
Vol 13 (31) ◽  
Author(s):  
R. W. HAY ◽  
R. BEMBI
1976 ◽  
Vol 29 (10) ◽  
pp. 2319 ◽  
Author(s):  
GA Lawrance ◽  
RW Hay

The macrocyclic complex trans-[Co(dtcd)(NO2)Br] [ClO4] (dtcd = 5,12-dimethyl-l,4,8,1l-tetraaza-cyclotetradeca-4,ll-diene) has been prepared and its hydrolysis kinetics investigated. At 25�C and 0.1 M HN03 the aquation occurs with kaq = 6.2 x 10-3 s-1 to give the trans-Co(dtcd)(NO2)- (OH2)]2+ cation. The activation parameters at 298 K are ΔH? = 75.0 kJ mol-1 and ΔS? = -35.6 J K-1 mol-1. Hydrolysis of the bromide in the pH range 7.5-8.8 follows the rate expression kobs = kaq + kOH[OH-]. At 25�C (I = 0.1 M, NaClO4) kOH = 1.21 x 103 1. mol-1 s-1 with the activation parameters for base hydrolysis being ΔH? = 74.2 kJ mol-1 and ΔS? = +63.2 J K-1 mol-1 at 298 K. Aquation and base hydrolysis of the bromo complex at 25�C occur at rates 14 and 5 times faster respectively than those previously reported for the analogous trans-[Co(dtcd)(NO2)Cl]+ complex, the acceleration being due to a more favourable entropy of activation in each case.


2020 ◽  
Author(s):  
Felix Kaspar ◽  
Peter Neubauer ◽  
Anke Kurreck

<div>Ask what an equilibrium can do for you:</div><div>Hydrolysis of pentose-1-phosphates leads to an apparent increase of the equilibrium conversion in nucleoside phosphorolysis reactions. This information can be leveraged via equilibrium thermodynamics to determine the hydrolysis kinetics of in situ generated sugar phosphates, which are known to be elusive and difficult to quantify.<br></div>


2013 ◽  
Vol 67 (4) ◽  
Author(s):  
Ahmad Mohamad ◽  
Mohamed Adam

AbstractThree ligands of 2-pyridinylmethylene-8-quinolinyl (L1), methyl-2-pyridinylmethylene-8-quinolinyl (L2), and phenyl-2-pyridinylmethylene-8-quinolinyl (L3), Schiff bases were synthesised by direct condensation of 8-aminoquinoline with 2-pyridinecarboxaldehyde, 2-acetylpyridine, or 2-benzoylpyridine. They coordinated to Fe(II) ion in a 1: 2 mole ratio followed by treatment with iodide ions affording complexes with a general formula [Fe(L)2]I2·2H2O, (L = L1, L2, or L3). Spectrophotometric evaluation of the kinetics of base catalysed hydrolysis of these complex cations was carried out with an aqueous solution of NaOH in different ratios of water/methanol binary mixtures. Kinetics of the hydrolysis followed the rate law (k 2[OH−] + k 3[OH−]2)[complex]. Reactivity trends and their rate constants were compared and discussed in terms of ligand structure and solvation parameters. The methanol ratio affects the hydrolysis as a co-solvent which was analysed into initial and transition state components. The increase in the rate constant of the base hydrolysis of Fe(II) complexes, as the ratio of methanol increases, is predominantly caused by the strong effect of the organic co-solvent on the transition states.


ChemInform ◽  
1987 ◽  
Vol 18 (47) ◽  
Author(s):  
Y. L. WANG ◽  
H. D. LEE ◽  
M. W. BEACH ◽  
D. W. MARGERUM

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