Reactivity of phosphate diesters doubly coordinated to a dinuclear Cobalt(III) complex: Dependence of the reactivity on the basicity of the leaving group

Journal of the American Chemical Society

Volumn 120, Issue 32, 1998, Pages 8079-8087

  Williams, Nicholas H ^a   Cheung, William ^b   Chin, Jik ^b  

^a UNIVERSITY OF SHEFFIELD   (United Kingdom)

^b MCGILL UNIVERSITY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

COBALT COMPLEX; ORGANOPHOSPHATE;

ARTICLE; ESTERIFICATION; HYDROLYSIS; METAL BINDING; MOLECULAR DYNAMICS; MOLECULAR INTERACTION;

EID: 0032547320     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja980660s     Document Type: Article

References (49)

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22. (8) The rate constant for formation of m-fluoro-p-nitrophenolate is not included in Figure 3 since C-F bond cleavage is expected to occur, and so the observed value is only a maximum rate. Nucleophilic aromatic substitution of chloride and phosphate is comparable for p-nitro-substituted aromatic rings (Kirby, A. J.; Jencks, W. P. J. Am. Chem. Soc. 1965, 87, 3217); for hydroxide attack at phosphorus diesters with p-nitrophenyl or poorer leaving groups, attack at phosphorus is much faster (Kirby, A. J.; Younas, M. J. Chem. Soc. B 1970, 1165, 1187). However, in protic solvents, F is substituted much more rapidly than Cl in o-and p-nitro-substituted aromatic rings (Briner, P. G.; Miller, J.; Liveris, M.; Lutz, P. G. J. Chem. Soc. 1954, 1265. Bolto, B. A.; Miller, J.; Williams, V. A. J. Chem. Soc. 1955, 2926) and is expected to dominate for methyl m-fluoro-p-nitrophenyl phosphate. We did not investigate this reaction further.
23. The rate constant for formation of m-fluoro-p-nitrophenolate is not included in Figure 3 since C-F bond cleavage is expected to occur, and so the observed value is only a maximum rate. Nucleophilic aromatic substitution of chloride and phosphate is comparable for p-nitro-substituted aromatic rings (Kirby, A. J.; Jencks, W. P. J. Am. Chem. Soc. 1965, 87, 3217); for hydroxide attack at phosphorus diesters with p-nitrophenyl or poorer leaving groups, attack at phosphorus is much faster (Kirby, A. J.; Younas, M. J. Chem. Soc. B 1970, 1165, 1187). However, in protic solvents, F is substituted much more rapidly than Cl in o-and p-nitro-substituted aromatic rings (Briner, P. G.; Miller, J.; Liveris, M.; Lutz, P. G. J. Chem. Soc. 1954, 1265. Bolto, B. A.; Miller, J.; Williams, V. A. J. Chem. Soc. 1955, 2926) and is expected to dominate for methyl m-fluoro-p-nitrophenyl phosphate. We did not investigate this reaction further.
24. The rate constant for formation of m-fluoro-p-nitrophenolate is not included in Figure 3 since C-F bond cleavage is expected to occur, and so the observed value is only a maximum rate. Nucleophilic aromatic substitution of chloride and phosphate is comparable for p-nitro-substituted aromatic rings (Kirby, A. J.; Jencks, W. P. J. Am. Chem. Soc. 1965, 87, 3217); for hydroxide attack at phosphorus diesters with p-nitrophenyl or poorer leaving groups, attack at phosphorus is much faster (Kirby, A. J.; Younas, M. J. Chem. Soc. B 1970, 1165, 1187). However, in protic solvents, F is substituted much more rapidly than Cl in o-and p-nitro-substituted aromatic rings (Briner, P. G.; Miller, J.; Liveris, M.; Lutz, P. G. J. Chem. Soc. 1954, 1265. Bolto, B. A.; Miller, J.; Williams, V. A. J. Chem. Soc. 1955, 2926) and is expected to dominate for methyl m-fluoro-p-nitrophenyl phosphate. We did not investigate this reaction further.
25. The rate constant for formation of m-fluoro-p-nitrophenolate is not included in Figure 3 since C-F bond cleavage is expected to occur, and so the observed value is only a maximum rate. Nucleophilic aromatic substitution of chloride and phosphate is comparable for p-nitro-substituted aromatic rings (Kirby, A. J.; Jencks, W. P. J. Am. Chem. Soc. 1965, 87, 3217); for hydroxide attack at phosphorus diesters with p-nitrophenyl or poorer leaving groups, attack at phosphorus is much faster (Kirby, A. J.; Younas, M. J. Chem. Soc. B 1970, 1165, 1187). However, in protic solvents, F is substituted much more rapidly than Cl in o-and p-nitro-substituted aromatic rings (Briner, P. G.; Miller, J.; Liveris, M.; Lutz, P. G. J. Chem. Soc. 1954, 1265. Bolto, B. A.; Miller, J.; Williams, V. A. J. Chem. Soc. 1955, 2926) and is expected to dominate for methyl m-fluoro-p-nitrophenyl phosphate. We did not investigate this reaction further.
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35. (16) Binding phosphate or carboxylate to two Co(III) centers has the same effect as a single protonation. (a) Edwards, J. D.; Foong, S.-W.; Sykes, A. G. J. Chem. Soc., Dalton Trans. 1973, 829. (b) Scott, K. L.; Green, M.; Sykes, A. G. J. Chem. Soc. A 1971, 3651.
36. Binding phosphate or carboxylate to two Co(III) centers has the same effect as a single protonation. (a) Edwards, J. D.; Foong, S.-W.; Sykes, A. G. J. Chem. Soc., Dalton Trans. 1973, 829. (b) Scott, K. L.; Green, M.; Sykes, A. G. J. Chem. Soc. A 1971, 3651.
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40. We assume a concerted mechanism based on the results of Hengge and Cleland (Hengge, A. C.; Cleland, W. W. J. Am. Chem. Soc. 1990, 112, 7421). These authors showed that hydroxide-catalyzed hydrolysis of phosphates with good leaving groups takes place by a concerted mechanism. According to the principle of microscopic reversibility, a weak nucleophile should also cleave phosphates by a concerted mechanism.
41. It is unlikely that the bridging oxide acts as a general base for the transesterification reaction since the basicity of the oxide is expected to be greater than the basicity of the alkoxide formed from 2.
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43. Järvinen, P. ; Oivanen, M.; Lönnberg, H. J. Org. Chem. 1991, 56, 5396. Rate constant extrapolated from the data given for UpU hydrolysis at 90 and 60 °C. Also see, Kuusela, S.; Lönnberg, H. J. Chem. Soc., Perkin Trans. 2 1994, 2109.
44. Järvinen, P. ; Oivanen, M.; Lönnberg, H. J. Org. Chem. 1991, 56, 5396. Rate constant extrapolated from the data given for UpU hydrolysis at 90 and 60 °C. Also see, Kuusela, S.; Lönnberg, H. J. Chem. Soc., Perkin Trans. 2 1994, 2109.
45. After statistical correction for two identical leaving groups. See: Kumamoto, J.; Cox, Jr., J. R.; Westheimer, F. H. J. Am. Chem. Soc. 1956, 78, 4858.
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48. a of ethylene glycol is 14.8 (Jencks, W. P.; Regenstein, J. Handbook of Biochemistry and Molecular Biology; CRC Press: Cleveland, 1976; p 159).
49. a values > 14.3, external hydroxide attack on the phosphate is favored over the internal oxide attack.