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17
-
-
33746596819
-
-
Also observed with 2-decanol
-
Also observed with 2-decanol.
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-
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18
-
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0010472440
-
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ten Brink, G.-J.; Arenas, I. W. C. E.; Sheldon, R. A. Adv. Synth. Catal. 2002, 344, 355.
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19
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4544248275
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Measured using β-deuterated benzyl alcohol: Steinhoff, B. A.; Guzei, I. A.; Stahl, S. S. J. Am. Chem. Soc. 2004, 126, 11268.
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0037028556
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2 in DMSO (reoxidation of reduced palladium initially proposed as rate-limiting: (a) Steinhoff, B. A.; Fix, S. R.; Stahl, S. S. J. Am. Chem. Soc. 2002, 124, 766.
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33745033768
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37
-
-
33746637392
-
-
note
-
We will use "reductive elimination" to describe the departure of acetic-acid from a Pd-hydride intermediate, although we feel this process is electronically closer to acid-base reactivity (a proton hopping from one pair of electrons on palladium to another on the free carboxylate oxygen) than to traditional reductive elimination (a single orbital changing in character from antibonding between two adjacent ligands to a metal lone-pair as the ligands form a bond).
-
-
-
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38
-
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11444250482
-
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Landis, C. R.; Morales, C. M.; Stahl, S. S. J. Am. Chem. Soc. 2004, 126, 16302.
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40
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25444454085
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Keith, J. M.; Nielsen, R. J.; Oxgaard, J.; Goddard, W. A., III. J. Am. Chem. Soc. 2005, 127, 13172.
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41
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4544377572
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Schatz, M.; Raab, V.; Foxon, S. P.; Brehm, G.; Schneider, S.; Reiher, M.; Holthausen, M. C.; Sundermeyer, J.; Schindler, S. Angew. Chem., Int. Ed. 2004, 43, 4360.
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Holthausen, M.C.7
Sundermeyer, J.8
Schindler, S.9
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43
-
-
43949164303
-
-
Ehlers, A. W.; Böhme, M.; Dapprich, S.; Gobbi, A.; Höllwarth, A.; Jonas, V.; Köhler, K. F.; Stegmann, R.; Veldkamp, A.; Frenking, G. Chem. Phys. Lett. 1993, 208, 111.
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Ehlers, A.W.1
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Veldkamp, A.9
Frenking, G.10
-
44
-
-
33746633189
-
-
note
-
Due to their instability relative to preceding states, accumulation of 6 and 7 will be negligible.
-
-
-
-
46
-
-
33746584616
-
-
note
-
1/2; i.e., barrier width is weighted more heavily than height.
-
-
-
-
47
-
-
33746600097
-
-
note
-
It may seem contradictory that there are three hydrogen-dominated modes in addition to the imaginary eigenvector. The motion along the reaction coordinate at TS2 is actually dominated by the ketone, as the O=C bond twists away from the Pd-H bond and a long hydrogen bond forms between a hydrogen on the substrate phenyl group and the free oxygen of the acetate ligand. The flatness of the PES near TS2 and the large mass of the ketone are responsible for the small magnitude of v‡.
-
-
-
-
48
-
-
33746603332
-
-
note
-
a, the assumption that liberated acid exists as dimers in solution does not affect these relations.
-
-
-
-
49
-
-
20444436397
-
-
Mercer, G. J.; Sturdy, M.; Jensen, D. R.; Sigman, M. S. Tetrahedron 2005, 61, 6418.
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Mercer, G.J.1
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Sigman, M.S.4
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51
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2442556459
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Schrödinger, L.L.C., Portland, OR, 1991-2003
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