Outer-sphere co-ordination and optical activity in transition-metal complexes

1965 ◽  
pp. 335 ◽  
Author(s):  
S. F. Mason ◽  
B. J. Norman
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Optical Activity ◽  
Transition Metal Complexes ◽  
Outer Sphere

Solvation of Coordinatively Saturated Metal Complexes of Nitrogen Ligands

1985 ◽  
Vol 40 (12) ◽  
pp. 1271-1277 ◽  
Author(s):  
A. N. Kitaigorodskii ◽  
A. N. Belyaev
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Organic Compounds ◽  
Transition Metal Complexes ◽  
Specific Interaction ◽  
Outer Sphere ◽  
Electrostatic Model ◽  
H Nmr ◽  
Nitrogen Ligands ◽  
Paramagnetic Shifts

1H NMR shifts were measured for ten organic compounds L in solutions containing paramagnetic bis[hydrotris(l-pyrazolyl)borato]cobalt(II), Co(HBpz3)2. The observed paramagnetic shifts were accounted for by pseudo-contact interactions in the outer-sphere adducts of Co(HBpz3)2 · L. From the concentration dependence of the induced shifts, the thermodynamic parameters of the outer-sphere complexation were determined. It is shown that a simple electrostatic model of Co(HBpz3)2 solvation is not consistent with the experimental results. Comparison of the data for pyrazolylborate and β-diketonate transition metal complexes showed that the specificity of the outer-sphere solvation depends to a large extent on the nature of the first coordination sphere ligands. Co(HBpz3)2 induces anomalous shifts of the signals of NMR standards. It is necessary to assume a specific interaction between the standards and Co(HBpz3)2.

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