The rate of substitution from η6-arene ruthenium(II) complexes

The rate and mechanism of substitution in the Ru(II) complexes (C1-C6) by thiourea nucleophiles was studied at pH 2 and rate constants measured as a function of nucleophile concentrations and temperature using spectrometric methods. There is increased electron density at the Ru metal atom of C2 as a result of inductive donation by substituents on the arene ligand, making it less positive and therefore less reactive than C1. For the complexes C3-C6 bearing the 2,2 '-bipyridyl ligand, the aqua ligands are located trans to the arene ligands, and hence, their reactivity increases in accordance to the number and type of alkyl substituents on the eta(6)-arene ligands which donate inductively into the pi-molecular orbitals, causing increased trans labialisation of the coordinated aquo co-ligand. Compared to the reactivity of triaquo complex (C1), the auxiliary bipyridyl ligand of (C3) complex lowers the rate of substitution for the later complex by a factor of about 100, possibly due to its steric hindrance at the Ru(II) metal centre. The significantly negative activation entropies and positive activation enthalpies suggest an associative mode of substitution. The reactivity of the nucleophiles follow the order DMTU > TU > TMTU.