Dissociative ligand substitution

In the kinetic trans effect, the departure of the trans ligand is probably aided by a stabilization of the transition state via the same mechanisms operative for the trans influence.114 Both associative and dissociative ligand substitution processes seem to be facilitated in this way.117... 

Louie, J., Hartwig, J. F. Transmetalation, Involving Organotin Aryl, Thiolate, and Amide Compounds. An Unusual Type of Dissociative Ligand Substitution Reaction. J. Am. Chem. Soc. 1995,117,11598-11599. 

Almost all of the reactions of metals can be classified into just a few typical reactions, and the reactions that metals promote in organic chemistry are simple combinations of these typical reactions. If you learn these typical reactions, you will have no trouble drawing metal-mediated mechanisms. The typical reactions of metal complexes are ligand addition/ligand dissociation/ligand substitution, oxidative addition/reductive elimination, insertion/j8-elimination, a-insertion/ a-elimination, cr-bond metathesis (including transmetallations and abstraction reactions), [2 + 2] cycloaddition, and electron transfer. 

Fig. 4.31. Dissociative ligand substitution reactions of (L)(PR3)(X)2Ru=CHR (L = PR3 or NHC) phosphine/phosphine and phosphine/olefin substitutions.

Dissociative ligand substitution reactions of 18-electron Pd(0) complexes... 

General Features of the Kinetics of Dissociative Ligand Substitution... 

Ligand substitution on the d , 18-electron, tetrahedral complex Ni(CO) is a classic example of a dissociative ligand substitution. - Kinetic studies show that the rate is first order in nickel and independent of [L]. These data are consistent with rate-determining dissociation of CO (Equation 5.21). 

The hydrosulfide ligand in [M(CO)5SH] (M = Cr or W) is a good cis labilizer, better than bromide and slightly weaker than acetate. The trans effect for the dissociative ligand substitution shown in equation (8) spans... 

---