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

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Abstract
X-Ray structural data for a,b-h,g -[Pt{ o -C 6 H 4 C(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 H 2 O ligand and the carbonyl carbon (O···C separation 3.47 Å) in the reactive complex [Pt{ o -C 6 H 4 C(Me) NOC( O)Me}py(OH)] generated in aqueous solution. References 1 (a) J. Chin Acc. Chem. Res. 24 1991 145 (b) N.N. Murthy K.D. Karlin H.H. Thorp V.L. Pecoraro Mechanistic Bioinorganic Chemistry 1995 American Chemical Society Washington DC 165 193 2 For recent representative reviews see (a) R.W. Hay G. Wilkinson Comprehensive Coordination Chemistry vol. 6 1986 Pergamon Press Oxford, New York 411 (b) J. Suh Acc. Chem. Res. 25 1992 273 (c) R. Breslow Pure Appl. Chem. 66 1994 1573 (d) R. Breslow Acc. Chem. Res. 28 1995 146 3 (a) I.E. Burgeson N.M. Kostić Inorg. Chem. 30 1991 4299 (b) L. Zhu N.M. Kostić Inorg. Chem. 31 1992 3994 (c) L. Zhu N.M. Kostić J. Am. Chem. Soc. 115 1993 4566 (d) L. Zhu N.M. Kostić Inorg. Chim. Acta 217 1994 21 (e) L. Zhu L. Qin T.N. Parac N.M. Kostić J. Am. Chem. Soc. 116 1994 5218 (f) N. Juranic V. Likić N.M. Kostić S. Macura Inorg. Chem. 34 1995 938 (g) T.N. Parac N.M. Kostić J. Am. Chem. Soc. 118 1996 51 4 E.V. Krooglyak G.M. Kazankov S.A. Kurzeev V.A. Polyakov A.N. Semenov A.D. Ryabov Inorg. Chem. 35 1996 4804 5 A.D. Ryabov G.M. Kazankov A.K. Yatsimirsky V.A. Polyakov L.G. Kuz’mina O.Yu. Burtseva N.A. Dvortsova Inorg Chem. 31 1992 3083 6 A.D. Ryabov L.G. Kuz’mina V.A. Polyakov G.M. Kazankov E.S. Ryabova M. Pfeffer R. van Eldik J. Chem. Soc., Dalton Trans. 1995 999 7 A.K. Yatsimirsky G.M. Kazankov A.D. Ryabov J. Chem. Soc., Perkin Trans. 2 1992 1295 8 H. Onoue K. Minami K. Nakagawa Bull. Chem. Soc. Jpn. 43 1970 3480 9 International Tables for X-Ray Crystallography , Kynoch Press, Birmingham, 1974, vol. 4. 10 A. Bondi J. Phys. Chem. 68 1964 441 11 (a) M.W. Schmidt K.K. Baldridge J.A. Boatz S.T. Elbert M.S. Gordon J.H. Jensen S. Koseki N. Matsunaga K.A. Nguyen S.J. Su T.L. Windus M. Dupuis J.A. Montgomery J. Comput. Chem. 14 1993 1347 (b) A.E. Reed R.B. Weinstock F. Weinhold J. Chem. Phys. 83 1985 735 (c) A.E. Reed L.A. Curtiss F. Weinhold Chem. Rev. 88 1988 899 12 A.V. Nemukhin I.A. Topol F. Weinhold Inorg. Chem. 34 1995 2980 13 M. Schmülling D.M. Grove G. van Koten R. van Eldik N. Veldman L. Spek Organometallics 15 1996 1384 14 W.P. Jencks Catalysis in Chemistry and Enzymology 1969 McGraw-Hill Book Company New York, London

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