Kinetics and Mechanism of the Formation of Palladium Bis(benzylamine) Complexes from Reaction of Benzylamine with Palladium Tri-o-tolylphosphine Mono(amine) Complexes

Inorganic Chemistry

Volumn 36, Issue 12, 1997, Pages 2610-2616

  Zhong, H Annita ^a   Widenhoefer, Ross A ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0006621645     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic961388v     Document Type: Article

References (69)

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16. eq = 0.57 at 55°C), a 35-fold excess of benzylamine relative to 2 was required to ensure ≥95% completion. As a result, the dependence of the rate on benzylamine concentration below <0.20 M could not determined under these conditions.
17. -1 at 65°C), approximately 5% of the magnitude of the second-order term. Although a nonzero intercept of the ordinate suggests the presence of a ligand-independent pathway, the large error associated with the intercept, particularly considering the lack of data at low amine concentrations, precludes this assignment. In addition, the temperature and solvent dependence of the intercept was inconsistent with the presence of an amine-independent pathway. Although an amine-independent pathway for conversion of 2 to 3 cannot be rigorously excluded, the mechanism of the conversion of 2 to 3 is clearly dominated by an associative pathway at all but very low benzylamine concentration.
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19. For related kinetics see: (a) Ohno, N.; Cusanovich, M. A. Biophys. J. 1981, 36, 589. (b) Pelizzetti, E.; Mentasti, E. Inorg. Chem. 1979, 18, 583. (c)Bosnich, B.; Dwyer, F. P.; Sargeson, A. M. Aust. J. Chem. 1966, 19, 2213. (d)Bosnich, B.; Dwyer, F. P. Aust. J. Chem. 1966, 19, 2051. (e) Butler, J.; Davies, D. M.; Sykes, A. G. J. Inorg. Biochem. 1981, 15, 41. (f) Below, J. F.; Connick, R. E.; Coppel, C. P. J. Am. Chem. Soc. 1958, 80, 2961.
20. For related kinetics see: (a) Ohno, N.; Cusanovich, M. A. Biophys. J. 1981, 36, 589. (b) Pelizzetti, E.; Mentasti, E. Inorg. Chem. 1979, 18, 583. (c)Bosnich, B.; Dwyer, F. P.; Sargeson, A. M. Aust. J. Chem. 1966, 19, 2213. (d)Bosnich, B.; Dwyer, F. P. Aust. J. Chem. 1966, 19, 2051. (e) Butler, J.; Davies, D. M.; Sykes, A. G. J. Inorg. Biochem. 1981, 15, 41. (f) Below, J. F.; Connick, R. E.; Coppel, C. P. J. Am. Chem. Soc. 1958, 80, 2961.
21. For related kinetics see: (a) Ohno, N.; Cusanovich, M. A. Biophys. J. 1981, 36, 589. (b) Pelizzetti, E.; Mentasti, E. Inorg. Chem. 1979, 18, 583. (c)Bosnich, B.; Dwyer, F. P.; Sargeson, A. M. Aust. J. Chem. 1966, 19, 2213. (d)Bosnich, B.; Dwyer, F. P. Aust. J. Chem. 1966, 19, 2051. (e) Butler, J.; Davies, D. M.; Sykes, A. G. J. Inorg. Biochem. 1981, 15, 41. (f) Below, J. F.; Connick, R. E.; Coppel, C. P. J. Am. Chem. Soc. 1958, 80, 2961.
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