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Trinuclear approach to hydrolyzing a phosphate diester
Journal of Inorganic Biochemistry
110
BIOINSPIRED HOMOGENEOUS CATALYSIS
241
TRINUCLEAR APPROACH TO HYDROLYZING A PHOSPHATE DIESTER
J. S. Seo, D. Williams, and J. Chin Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Canada H3A-2K6 In order to hydrolyze the phosphate diester bond of DNA within few seconds, a catalyst must provide enormous rate-accelerations (> 1016 fold). There are three principal modes of activations that a metal ion can provide for accelerating the rate of phosphate ester hydrolysis [1]. They are Lewis acid activation (coordination of phosphoryl oxygen(s) to the metal) nucleophile activation (coordination of a nucleophile such as a hydroxide or an oxide to the metal) and leaving group activation (coordination of the leaving group to the metal). Interactions between the three modes of activations in a trinuclear approach to hydrolyzing a phosphate diester will be investigated in a systematic way using substitutionally inert Co(HI) and Pt(II) complexes. The main focus of this investigation is on dissecting and quantifying the modes of action that metal ions can provide with particular emphasis on the cooperativity of the metal ions. 1. (a) Wahnon, D.; Lebuis, A. -M.; Chin, J. Angew. Chem. Int. Ed. Engl. 1995, 34, 2412. (b) Young, M. J.; Chin, J. J. Am. Chem. Soc. 1995, 117, 10577. (c) Williams, N.; Chin, J. J. Chem. Soc. Chem. Commun. 1996, 131. (d) Hurst, P.; Takasaki, B. K.; Chin, J. J. Am. Chem. Soc. 1996, 118, 9982. (e) Seo, J. S.; Sung, N.-D., Hynes, R. C.; Chin, J. Inorg. Chem. 1996, 35, 7472.
110
BIOINSPIRED HOMOGENEOUS CATALYSIS
241
TRINUCLEAR APPROACH TO HYDROLYZING A PHOSPHATE DIESTER
J. S. Seo, D. Williams, and J. Chin Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Canada H3A-2K6 In order to hydrolyze the phosphate diester bond of DNA within few seconds, a catalyst must provide enormous rate-accelerations (> 1016 fold). There are three principal modes of activations that a metal ion can provide for accelerating the rate of phosphate ester hydrolysis [1]. They are Lewis acid activation (coordination of phosphoryl oxygen(s) to the metal) nucleophile activation (coordination of a nucleophile such as a hydroxide or an oxide to the metal) and leaving group activation (coordination of the leaving group to the metal). Interactions between the three modes of activations in a trinuclear approach to hydrolyzing a phosphate diester will be investigated in a systematic way using substitutionally inert Co(HI) and Pt(II) complexes. The main focus of this investigation is on dissecting and quantifying the modes of action that metal ions can provide with particular emphasis on the cooperativity of the metal ions. 1. (a) Wahnon, D.; Lebuis, A. -M.; Chin, J. Angew. Chem. Int. Ed. Engl. 1995, 34, 2412. (b) Young, M. J.; Chin, J. J. Am. Chem. Soc. 1995, 117, 10577. (c) Williams, N.; Chin, J. J. Chem. Soc. Chem. Commun. 1996, 131. (d) Hurst, P.; Takasaki, B. K.; Chin, J. J. Am. Chem. Soc. 1996, 118, 9982. (e) Seo, J. S.; Sung, N.-D., Hynes, R. C.; Chin, J. Inorg. Chem. 1996, 35, 7472.