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The comparative chemistry of ammine and methylamine complexes of rhodium(III) and cobalt(III)

For the aquation of (CH3NH2)5RhCl2+, the first order rate coefficients are represented by ΔHaq* = 101.9 kJ mol−1 and ΔSaq* = −50.2 JK−1 mol−1 in 0.1 M HClO4, while for base hydrolysis the rate is first order in [(CH3NH2)5RhCl2+] and [OH−] at ionic strength 0.10 M and the rate coefficients (in M−1 s−1) are represented by ΔHOH*> = 108.6 kJ mol−1 and ΔSOH* = 74.1 J K−1 mol−1. Acid dissociation constants are reported for (RNH2)5MOH23+ (R = H or CH3; M = Rh or Co), and these, combined with spectral data, show CH3NH2 to be a poorer electron donor than NH3 in complexes of this type, contrary to expectations. The comparative kinetics of reactions of (RNH2)5MCl2+ support the assignment of an Ia mechanism to aquation when M = Rh or Cr, Id to aquation when M = Co, and Dcb for base hydrolysis in all these cases.