The nature of biomimetically relevant rate enhancement of hydrolysis in a coordination sphere of square-planar metal complexes suggested by an X-ray structural study of a,b-h,g[Pt{o-C6H4C(Me)=NOC(=O)Me}(μ-Cl)]2

Mendeleev Communications Pub Date: DOI: 10.1070/MC1997v007n04ABEH000757

Abstract

X-Ray structural data for a,b-h,g-[Pt{o-C6H4C(Me)=NOC(=O)Me}(μ-Cl)]2 and ab initio quantum chemical calculations were used to show that the biomimetic hydrolysis of esters and amides within the coordination sphere of a square-planar complex, in general, and the deacylation of cyclometallated aryl oxime esters, in particular, is due to the stereochemical control which arises from the close proximity of the coordinated OH or H2O ligand and the carbonyl carbon (O...C separation 3.47?) in the reactive complex [Pt{o-C6H4C(Me)=NOC(=O)Me}py(OH)] generated in aqueous solution.

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