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Science 18 April 1969:
Vol. 164. no. 3877, pp. 320 - 321
DOI: 10.1126/science.164.3877.320

Articles

Metal Ion Activation of Phosphate Transfer by Bidentate Coordination

Francis J. Farrell 1, William A. Kjellstrom 1, and Thomas G. Spiro 1

1 Department of Chemistry, Princeton University, Princeton, New Jersey 08540

The hydrolysis of methyl phosphate bound to the triethylenetetramine-cobalt(III) ion is much faster than the hydrolysis of either dimethyl phosphate bound to the same cation or methyl phosphate bound to the pentamminecobalt-(III) ion. The rate enhancement is attributed to bidenate coordination of the methyl phosphate. This feature suggests a pseudorotation mechanism analogous to that proposed by Westheimer for the hydrolysis of ethylene methyl phosphate. Stabilization of bidentate coordination might play a role in metal ion activation of phosphate-transfer enzymes.





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Science. ISSN 0036-8075 (print), 1095-9203 (online)