Reactivity trend seen in the reduction of transition metal complexes by outer-sphere reactants verified for hydrated Pulse radiolysis studies of cobalt(III) complexes

1971 ◽  
Vol 10 (9) ◽  
pp. 1999-2002 ◽  
Author(s):  
G. D. Venerable
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Pulse Radiolysis ◽  
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.

Structure of the Second Coordination Sphere of Transition Metal Complexes. IV. Solvent Effects

1973 ◽  
Vol 51 (24) ◽  
pp. 4137-4139 ◽  
Author(s):  
D. R. Eaton ◽  
K. L. Chua
Keyword(s):  
Dipole Moment ◽  
Carbon Tetrachloride ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Coordination Sphere ◽  
Solvent Effects ◽  
Equilibrium Constants ◽  
Outer Sphere ◽  
Second Coordination Sphere

The participation of various solvents in the second coordination sphere of Co(II) pyrazolylborate has been investigated. Equilibrium constants relative to carbon tetrachloride as a second sphere ligand have been obtained. The ability of a solvent to participate in the second sphere depends predominantly on its dipole moment and it is concluded that Van der Waals forces are responsible for outer sphere binding.

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