Kinetics of aquation of aquopentachlororhodium(III) and chloride anation of diaquotetrachlororhodium(III) anions

The fundamental flaw of the HSAB principle is revealed by a complete speciation analysis of the [PtCl6−nBrn]2−(n = 0–6) system

“…The good least-squares non-linear fits obtained illustrated in Fig. 3 coupled with the exceptional agreement of the DG 0 rxn b 10 ð Þ s values (À31.94 and À33.6 kJ mol À1 ) with two independent methods (IP-HPLC-UV-vis and electrochemically) and taking into consideration the result obtained with the ECE, eqn (17), convincingly demonstrate the accuracy of our calculated thermodynamic parameters for this system. In light of the above results, the assumption concerning the use of species concentrations and not species activity for equilibrium constant calculations are well justified.…”

“…the kinetic trans effect can cause a concentration build-up of only one stereoisomer due to the relatively slow rate of ligand exchange reactions that should increase the concentration of the other stereoisomer in a pair. [15][16][17][18] Inspection of Fig. 2 (1)…”

“…. The overall changes in standard reaction Gibbs energy for the two reaction paths are equal, yielding the energy conservation relationship eqn (17). Several energy conservation equations (ECE's) can be derived for this system, of which eqn (17) is one example for an 8 member inorganic reaction 'loop'.…”

“…There are multiple paths by which one Pt IV chlorido bromido complex can be converted into another, e.g. (17). Several energy conservation equations (ECE's) can be derived for this system, of which eqn (17) is one example for an 8 member inorganic reaction 'loop'.…”

“…(17). Several energy conservation equations (ECE's) can be derived for this system, of which eqn (17) is one example for an 8 member inorganic reaction 'loop'. It should be pointed out that whilst calculating the various b i , using the program EquiState, no ECEs were used.…”