Synthesis and Reactions of Transition Metal Complexes Handout 5 The trans-influence Dont confuse the trans-effect with the

e trans-influence, which is a phenomenon where the trans ligand influences the M-L bond strength of the ligand opposite. Note that this is a thermodynamic phenomenon affecting the bond energy. It is not a kinetic phenomenon like the trans-effect and is not directly giving information on (substitution) reaction rates. The general trend is that a stronger sigma-donor ligand will have a larger trans-influence. Other factors related to bond strength are also affected, e.g. M-L vibration frequency is lower with weaker bonds; 1J (Pt-P) NMR coupling constants are smaller with weaker bonds. For information only..the mechanism for the binding of Cisplatin to DNA provides an extremely important real-world example of the need to understand the kinetics of substitution at square-planar metal complexes.

Ligand substitution at octahedral complexes Understanding ligand substitution at octahedral complexes is of prime importance since this is by far the most common geometry of transition metal complexes. Beyond the transition metal series, it is also very common in the s- and p-block elements e.g. SF 6 , SiF 6 2-, [Mg(OH 2 ) 6 ]2+ so its importance is very general. Substitution at octahedral complexes almost always occurs by the interchange (I) mechanism. The key question is therefore whether the rate determining step is associative (I a , i.e. formation of the new MY bond) or dissociative (I d , i.e. breaking of the old MX bond) since both mechanisms are common. Many studies have shown examples of a dissociative rate-determining step, however in the case of a large central ion (e.g. 4d or 5d) or a metal with few d-electrons, associative behaviour becomes more significant. Since the mechanism will have an effect on the stereochemistry of products, it is important to understand which mechanism is operating.

Example I d mechanism and the consequences on stereochemistry

Reactions rates and associative/dissociative mechanisms are affected differently by a number of factors: the d-electron configuration of the metal via the crystal-field activation energy (CFAE) the difference between the CFSE of the ground and transition states. the nature of the incoming ligand the nature of the leaving group the spectator ligands both steric and electronic effects the charge of the metal complex the effect of acids and bases - acids can accelerate the rate of substitution by protonation of the leaving group and bases can accelerate the rate of substitution by stabilising the 5coordinate TS in the case of a dissociative mechanism