SUBSTITUTION AT OCTAHEDRAL CENTERS: II. EFFECT OF SALTS UPON THE RATE OF HYDROLYSIS OF THE HALOPENTAMMINECHROMIUM(III) IONS

1961 ◽  
Vol 39 (11) ◽  
pp. 2371-2379 ◽  
Author(s):  
T. P. Jones ◽  
W. E. Harris ◽  
W. J. Wallace

A study of the hydrolysis of the halopentamminechromium(III) ions in the presence of the sodium salts of weak acids reveals a rate acceleration due to specific ion-pair formation. The acceleration is due partly to a charge-transfer effect and partly to the fact that the ion helps to maintain the octahedral configuration of the complex in the transition state. It is concluded that the reaction occurs by dissociation, but without collapse of the structure to a five-co-ordinated intermediate.

1988 ◽  
Vol 92 (7) ◽  
pp. 1703-1705 ◽  
Author(s):  
R. J. Locke ◽  
Steve H. Modiano ◽  
E. C. Lim

2020 ◽  
Vol 32 (6) ◽  
pp. 1379-1383
Author(s):  
L. Devaraj Stephen ◽  
S.G. Gunasekaran ◽  
M. Soundarrajan

Reduction of CoIII centre in CoIII(pn)2(Cl)(L)2+ with reference to solvent medium and structure of the complex via ion pair charge transfer (IPCT) paves way for the novel reaction mechanism route. In this work, we prepared, characterized and photoinduced the complexes CoIII(pn)2(Cl)(L)2+ (where L = RC6H4NH2, R = m-OMe, p-F and H) in the presence of iodide ion. Quantum yield for 254 nm excitation of CoIII(pn)2(Cl)(L)2+(where L = RC6H4NH2, R = m-OMe, p-F and H) in water-1,4-dioxane mixtures (Diox = 0, 5, 10, 15, 20, 25, and 30% (v/v)) were also derived for all the complexes in presence of added iodide ion, in which CoIII was reduced via [CoIII(pn)2(Cl)(L)2+….. I-] ion-pair formation. The photoinduced state is ion-pair charge transfer transition state and the quantum efficiency is solvent reliant and they are non-reactive. That is, change in ΦCo(II) is dependable with observed increase in xDiox of the mixed solvent medium. Correlation analysis using empirical parameters εr, Y, ET N and DNN provides a model to understand the solvent medium participation and interaction. This work gains an insight into the role of aqueous-organic solvent medium in CoIII(pn)2(Cl)(L)2+ photoreduction, which may be of great significance in developing novel approaches in the field of high performance catalysis


2018 ◽  
Vol 98 (1) ◽  
Author(s):  
Shekhar Bag ◽  
Shatabda Bhattacharya ◽  
Diptiman Dinda ◽  
M. V. Jyothirmai ◽  
Ranjit Thapa ◽  
...  

2010 ◽  
Vol 55 (7) ◽  
pp. 2463-2469 ◽  
Author(s):  
Yoshihiro Kudo ◽  
Daisuke Todoroki ◽  
Naoki Horiuchi ◽  
Shoichi Katsuta ◽  
Yasuyuki Takeda

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