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accepted, DOI: 10.1002/anie.200503663
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(e) Jiang, X.-B.; Lefort, L.; Goudriaan, P. E.; de Vries, A. H. M.; van Leeuwen, P. W. N. M.; de Vries, J. G.; Reek, J. N. H. Angew. Chem., Int. Ed. 2005, 44, accepted, DOI: 10.1002/anie.200503663.
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Angew. Chem., Int. Ed.
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Jiang, X.-B.1
Lefort, L.2
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De Vries, A.H.M.4
Van Leeuwen, P.W.N.M.5
De Vries, J.G.6
Reek, J.N.H.7
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For reviews see: (a) Wilkinson, M. J.; van Leeuwen, P. W. N. M.; Reek, J. N. H. Org. Biomol. Chem. 2005, 3, 2371-2383.
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(a) Freixa, Z.; Beentjes, M. S.; Batema, G. D.; Dieleman, C. B.; van Strijdonck, G. P. F.; Reek, J. N. H.; Kamer, P. C.; Fraanje, J.; Goubitz, K.; van Leeuwen, P. W. N. M. Angew. Chem., Int. Ed. 2003, 42, 1284.
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Freixa, Z.1
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33644507650
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note
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The structures of the complexes were generated using TITAN and were optimized using DFT optimization (B3LYP, 6-3IG**).
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28
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For select examples: (a) Bondy, C. R.; Gale, P. A.; Loeb, S. J. J. Am. Chem. Soc. 2004, 126, 5030.
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Beer, P.D.1
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We have analyzed the titration curves with a fitting program developed by Hunter et al.: Bisson, A. P.; Hunter, C. A.; Carlos, J.; Young, K. Chem. Eur. J. 1998, 4, 845.
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17444402783
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An example of an anion-templated cis hydrogen-bonded system was recently reported: Lu, X.-X.; Tang, H.-S.; Ko, C.-C.; Wong, J. K.-Y.; Zhu N.; Yam, V. W.-W. Chem. Commun. 2005, 1572.
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41
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33644521140
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note
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31P NMR spectrum due to the equilibrium between these three species.
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-
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42
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33644517795
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note
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1H NMR spectrum, and it is believed to be due to decomposition of 4 that ultimately occurs in solution over several days.
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-
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43
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33644510966
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note
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2PdMeCl was identified by comparison with a separate NMR tube experiment.
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44
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0034641226
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Shultz, C. S.; Ledford, J.; DeSimone, J. M.; Brookhart, M. J. Am. Chem. Soc. 2000, 122, 6351.
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-
45
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33644522624
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note
-
The major species present in solution (between -80 and -40°C) is the four-coordinate CO-adduct, which was followed by variable-temperature NMR spectroscopy, and it formed the acetyl complex. Below -70°C, an unidentifiable minor species is observed in solution, and this complex is a potential intermediate that ultimately results in the formation of the acetyl product.
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46
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0038613013
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van Leeuwen, P. W. N. M.; Zuideveld, M. A.; Swennenhuis, B. H. G.; Freixa, Z.; Kamer, P. C. J.; Goubitz, K.; Fraanje, J.; Lutz, M.; Spek, A. J. Am. Chem. Soc. 2003, 125, 5523
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Van Leeuwen, P.W.N.M.1
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Kamer, P.C.J.5
Goubitz, K.6
Fraanje, J.7
Lutz, M.8
Spek, A.9
-
47
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33644504751
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note
-
Since the CO and methyl groups should be arranged cis with respect to one another for facile migratory insertion to occur and these palladium complexes were never observed in this coordination mode, the carbonylation must occur immediately upon rearrangement to the cis species, which is followed by a successive rearrangement to the thermodynamic trans-acetyl product.
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48
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33751385318
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Rülke, R. E.; Ernsting, J. M.; Spek, A. L.; Elsevier, C. J.; van Leeuwen, P. W. M. N.; Vrieze, K. Inorg. Chem. 1993, 32, 5769.
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Elsevier, C.J.4
Van Leeuwen, P.W.M.N.5
Vrieze, K.6
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0036328843
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Bacchi, A.1
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Pelizzi, G.4
Pelagatti, P.5
Ugolotti, S.6
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