THE NATURE OF BIOMIMETICALLY RELEVANT RATE ENHANCEMENT OF HYDROLYSIS IN A COORDINATION SPHERE OF SQUARE-PLANAR METAL-COMPLEXES SUGGESTED BYAN X-RAY STRUCTURAL STUDY OF A,B-H,G-[PT(O-C6H4C(ME)=NOC(=O)ME)(MU-CL)](2)
Gm. Kazankov et al., THE NATURE OF BIOMIMETICALLY RELEVANT RATE ENHANCEMENT OF HYDROLYSIS IN A COORDINATION SPHERE OF SQUARE-PLANAR METAL-COMPLEXES SUGGESTED BYAN X-RAY STRUCTURAL STUDY OF A,B-H,G-[PT(O-C6H4C(ME)=NOC(=O)ME)(MU-CL)](2), Mendeleev communications, (4), 1997, pp. 159-162
X-Ray structural data for a,b-h,g-[Pt(o-C6H4C(Me)=NOC(=O)Me)(mu-Cl)](2
) and ab initio quantum chemical calculations were used to show that t
he 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 stereo
chemical control which arises from the close proximity of the coordina
ted OH or H2O ligand and the carbonyl carbon (O ... C separation 3.47
Angstrom) in the reactive complex [Pt{o-C6H4C(Me)=NOC(=O)Me}py(OH)] ge
nerated in aqueous solution.