The Effect of the "Inert" Counteranions in the Deprotonation of the Dihydrogen Complex trans-[FeH(η2-H2)(dppe) 2]+: Kinetic and Theoretical Studies

Journal of the American Chemical Society

Volumn 126, Issue 8, 2004, Pages 2320-2321

  Basallote, Manuel G ^a   Besora, Maria ^b   Durán, Joaquín ^a   Fernández Trujillo, M Jesús ^a   Lledós, Agustí ^b   Angeles Manez M ^a   Maseras, Feliu ^b  

^a UNIVERSITY OF CÁDIZ   (Spain)

^b UNIVERSITAT AUTÒNOMA DE BARCELONA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ANION; HYDROGEN; IRON COMPLEX;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; PROTON TRANSPORT; THEORY;

EID: 1542375005     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja039844j     Document Type: Article

References (21)

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3. (c) Macchioni, A.; Zuccaccia, C.; Clot, E.; Gruet, K.; Crabtree, R. H. Organometallics 2001, 20, 2367.
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7. (a) Morris, R. H. In Recent Advances in Hydride Chemistry; Peruzzini, M., Poli, R., Eds.; Elsevier: Amsterdam, 2001; Chapter 1, pp 1-38.
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9. (c) Kubas, G. J. Metal Dihydrogen and σ-Bond Complexes; Kluwer Academic/Plenum Publishers: New York, 2001; pp 270-284.
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14. These observations are coincident with a previous report showing the absence of intermediates during deprotonation of 1: Cappellani, E. P.; Drouin, S. D.; Jia, G.; Maltby, P. A.; Morris, R. H.; Schweitzer, C. T. J. Am. Chem. Soc. 1994, 116, 3375. The reverse reaction, i.e., protonation of 2 to form 1, also occurs without accumulation of any intermediate: Basallote, M. G.; Durán, J.; Fernández-Trujillo, M. J.; Máñez, M. A. J. Chem. Soc., Dalton Trans. 1998, 2205.
15. These observations are coincident with a previous report showing the absence of intermediates during deprotonation of 1: Cappellani, E. P.; Drouin, S. D.; Jia, G.; Maltby, P. A.; Morris, R. H.; Schweitzer, C. T. J. Am. Chem. Soc. 1994, 116, 3375. The reverse reaction, i.e., protonation of 2 to form 1, also occurs without accumulation of any intermediate: Basallote, M. G.; Durán, J.; Fernández-Trujillo, M. J.; Máñez, M. A. J. Chem. Soc., Dalton Trans. 1998, 2205.
16. Wilkins, R. G. Kinetics and Mechanism of Reactions of Transition Metal Complexes, 2nd ed.; VCH: Weinheim, 1991; p 113.
17. - salt of 1 in the absence of additives were also unsuccessful.
18. 1min but leads to longer correlation times, in agreement with formation of association complexes: Guari, Y.; Ayllon, J. A.; Sabo-Etienne, S.; Chaudret, B.; Hessen, B. Inorg. Chem. 1998, 37, 640.
19. DFT calculations with the B3LYP functional. Computational details are given in the Supporting Information.
20. The kinetic features are also different in both cases. For the Mo complex, deprotonation is accelerated by small anions, but the rate law changes from a first-order dependence on the concentration of base to a first-order dependence on the anion concentration. In contrast, deprotonation of 1 is accelerated because of an increase of the second-order rate constant: (a) Hanckel, J. M.; Darensbourg, M. Y. J. Am. Chem. Soc. 1983, 105, 6979.
21. (b) Darensbourg, M. Y.; Ludvig, M. M. Inorg. Chem. 1986, 25, 2894.