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Table 2 Second-order rate constants, k2 , at different temperatures.
Reaction conditions: [MoO2Cl2{p-tolyl(CH3DAB)}] ¼ 5.0 ꢃ 10ꢀ4 M,
solvent ¼ CH3CN with less than 1% of decane
3
T/ꢁC
10ꢀ1 k2/molꢀ1 dm3 sꢀ1
4
5
G. Wahl, D. Kleinhenz, A. Schorm, J. Sundermeyer, R.
Stowasser, C. Rummey, G. Bringmann, C. Fickert and W. Kiefer,
Chem.-Eur. J., 1999, 5, 3237.
(a) A. D. Lopes, Ph.D. Thesis, ITQB/Universidade Nova de
Lisboa, Portugal, 1999; (b) A. M. Santos, Ph.D. Thesis,
25
40
50
60
0.330
0.880
1.40
3.00
Technischen Universita¨t Munchen, Germany, 2000; (c) J. J.
¨
Haider, Ph.D. Thesis, Technischen Universita¨t Munchen,
Germany, 1999.
¨
6
(a) W. A. Herrmann, G. M. Lobmaier, T. Priermeier, M. R.
Mattner and B. Scharbert, J. Mol. Catal. A: Chem., 1997, 117,
455; (b) R. Clarke, M. Gahagan, R. K. Mackie, D. F. Foster,
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7
(a) F. E. Kuhn, E. Herdtweck, J. J. Haider, W. A. Herrmann, I. S.
¨
Gonc¸alves, A. D. Lopes and C. C. Roma˜o, J. Organomet. Chem.,
1999, 583, 3; (b) F. E. Kuhn, A. D. Lopes, A. M. Santos, E.
¨
Herdtweck, J. J. Haider, C. C. Roma˜o and A. G. Santos,
J. Mol. Catal. A: Chem., 2000, 151, 147; (c) F. E. Kuhn, A. M.
¨
Santos, A. D. Lopes, I. S. Gonc¸alves, E. Herdtweck and C. C.
Roma˜o, J. Mol. Catal. A: Chem., 2000, 164, 25; (d ) F. E. Kuhn,
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A. M. Santos, I. S. Gonc¸alves, C. C. Roma˜o and A. D. Lopes,
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8
(a) W. A. Herrmann, J. J. Haider, J. Fridgen, G. M. Lobmaier
and M. Spiegler, J. Organomet. Chem., 2000, 603, 69; (b) S.
Bellemin-Laponnaz, K. S. Coleman, P. Dierkes, J.-P. Masson
and J. A. Osborn, Eur. J. Inorg. Chem., 2000, 1645; (c) F. E.
Fig. 9 Fit of the second-order rate constants, k2 , to the Eyring equation.
Reaction conditions: [MoO2Cl2{p-tolyl(CH3DAB)}] ¼ 5.0 ꢃ 10ꢀ4 M,
solvent ¼ CH3CN with less than 1% of decane.
Kuhn, A. M. Santos, A. D. Lopes, I. S. Gonc¸alves, J. E.
´
¨
Rodrıguez-Borges, M. Pillinger and C. C. Roma˜o, J. Organomet.
Chem., 2001, 621, 207; (d ) I. S. Gonc¸alves, F. E. Kuhn, A. M.
dioxomolybdenum(VI) complexes.10 Cyclooctene epoxidation
with [MoO2Cl2{p-tolyl(CH3DAB)}] includes a number of
simultaneous and consecutive elementary reactions. The cata-
lyst precursor–oxygen donor complex formation is first-order
dependent on TBHP and on the metal complex [MoO2Cl2{p-
tolyl(CH3DAB)}]. The oxidizing agent TBHP is transformed
to tert-butyl alcohol during the course of the reaction, which
can coordinate to the metal centre and consequently retard
the reaction. The initial rate of reaction of cyclooctene epoxida-
tion exhibits a first-order dependence with respect to initial
cyclooctene concentration and a fractional (0.64) reaction rate
order dependence with respect to initial concentration of TBHP.
¨
Santos, A. D. Lopes, J. E. Rodrıguez-Borges, M. Pillinger, P.
´
Ferreira, J. Rocha and C. C. Roma˜o, J. Organomet. Chem.,
2001, 626, 1; (e) A. A. Valente, I. S. Gonc¸alves, A. D. Lopes,
´
J. E. Rodrıguez-Borges, M. Pillinger, C. C. Roma˜o, J. Rocha
and X. Garcıa-Mera, New J. Chem., 2001, 25, 959.
´
9
A. M. Santos, F. E. Kuhn, K. Bruus-Jensen, I. Lucas, C. C.
¨
Roma˜o and E. Herdtweck, J. Chem. Soc., Dalton Trans., 2001,
1332.
´
10 F. E. Kuhn, M. Groarke, E. Bencze, E. Herdtweck, A. Prazeres,
¨
A. M. Santos, M. J. Calhorda, C. C. Roma˜o, I. S. Gonc¸alves,
A. D. Lopes and M. Pillinger, Chem.-Eur. J., 2002, 8,
2370.
11 M. Groarke, I. S. Gonc¸alves, W. A. Herrmann and F. E. Kuhn,
¨
J. Organomet. Chem., 2002, 649, 108.
12 (a) G. N. Schrauzer, L. A. Hughes, N. Strampach, P. R. Robinson
and E. O. Schlemper, Organometallics, 1982, 1, 44; (b) G. N.
Schrauzer, E. O. Schlemper, N. H. Liu, Q. Wang, K. Rubin, X.
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Acknowledgements
This work was partly funded by the FCT, POCTI and FEDER
(Project POCTI//QUI/37990/2001). AAV and MP thank the
FCT for post-doctoral grants and CN thanks the University
of Aveiro for a research grant. The authors are grateful to
Prof. Joa˜o Rocha for generous support.
13 R. Colton and I. B. Tomkins, Aust. J. Chem., 1965, 18, 447.
14 H. L. Kraus and W. Huber, Chem. Ber., 1961, 94, 2864.
15 G. van Koten and K. Vrieze, Adv. Organomet. Chem., 1982,
21, 151.
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313