Chemistry of the outer-sphere complexes

Mechanistic information from the effect of pressure on the kinetics of some anation reactions of aquopentaamminecobalt(III), -rhodium(III), and -chromium(III) ions in acidic aqueous solution

“…In this respect, our results emphasize the importance of estimating the ion-pair formation constant under the same experimental conditions as were employed in the kinetic study. 79 It is known that ion-pair formation constants decrease substantially on increasing the ionic strength (see eq 5), so that investigations carried out at lower ionic strength would improve the probability of detecting and accurately determining the value of Kx kinetically.19…”

Halide Ion Embraces in Tris(2,2′-bipyridine)metal Complexes

“…The structural studies of Nassimbeni have been particularly important in identifying the commonest types of interactions and provide a solid body of evidence for the hydrogen-bonding interactions with Werner-type coordination compounds [59][60][61][62][63][64][65]. Studies such as these relate directly to the "outer-sphere" complexes implicated in studies of substitution mechanisms, in which the incoming ligands are non-covalently associated with the starting complexes (A-type mechanisms) or intermediates (D-type mechanisms) [66,67]. Of particular importance are kinetic and thermodynamic studies, establishing both the nature and strength of the outer-sphere interactions between the oligopyridine complexes and halides and their relevance to the reaction chemistry of these species [68][69][70][71][72][73][74][75][76][77][78].…”

Outer sphere complexes as intermediates in coordination chemistry

“…That by Beck [18] was concerned largely with ionic complexes. It contains an extensive tabulation of the formation constants available at the time of publication and a description of the experimental methods used to measure these constants.…”