Monodentate ligands mechanism

The P-H oxidative addition, acrylonitrile insertion, and C-H reductive elimination steps were observed directly with the dcpe catalyst, and the potential intermediates Pt(diphos)(PHMes )(CH2CH2CN) (7, diphos = dppe, dcpe) were shown not to undergo P-C reductive elimination. The generality of this proposed mechanism for less bulky phosphine substrates, or for Pt catalysts supported by monodentate ligands, remains to be investigated [9]. 

For such a mechanism, the overall second-order formation rate constant is given by the product of the first-order constant ktx and the equilibrium constant Kos. The characteristic solvent exchange rates are thus often useful for estimating the rates of formation of complexes of simple monodentate ligands but, as mentioned already, in some cases the situation for macrocyclic and other polydentate ligands is not so straightforward. 

The first step in oxygen transfer is ligand substitution at an oxorhenium(V) center, Eq. (14). The final step (see Scheme 2, step 2) very likely is also ligand substitution. We have therefore examined the kinetics and mechanism of several reactions in which one monodentate ligand displaces another, represented in general as follows ... 

A corresponding reaction of acetate ion with AJP is also catalyzed by a bivalent metal ion. The reaction probably results in the formation of an acyl phosphate, which has not been identified as such but has been identified by trapping of the product with hydroxylamine. The best catalyst is beryllium ion, which catalyzes optimally at molar ratios of 1 to 1 or less. Acetate ion is presumably the reactive species, since the pH optimum of the reaction is 5. It is concluded from the pH effects in this study and in the transphosphorylation reaction that a complex of the metal ion and nucleophile must occur. Since acetate ion is a monodentate ligand, the mechanism postulated for the phosphorylation reaction above cannot be completely applicable to this case (36). 

For example, the differences between CP and Br in complexes of the type [Ru (r 6-arene)(en)Z]+, where arene is biphenyl, indane or benzene, is not dramatic, however, when Z = I the hydrolysis is slower (3- to 7-fold). Other leaving groups such as pyridine or pyridine derivatives can slow down the hydrolysis further and even block it almost completely on biologically-relevant time scales. Such complexes are not cytotoxic towards cancer cells within 24-h drug exposures. There are a few exceptions such as [Ru(ri6-hexamethylbenzene)(en)(SPh)]PF6, where the monodentate ligand is thiophenolate. This complex does not hydrolyse, but intrigu-ingly is active. The mechanism of activation of this complex is different (vide infra). 

Besides these monodentate ligands, many multidentate ones have been prepared and used in different fields of chemistry and only a few should be mentioned here. Rigid bidentate benzimidazole-based N-heterocyclic carbenes were successfully used to synthesize main-chain conjugated organometallic polymers 23, an interesting class of materials with desirable electronic and mechanical properties (Fig. 9) [110]. 

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