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All computations in this study have been performed using the Gaussian03 suite of programs.13 To include electron correlation at a reasonable computational cost, density functional theory (DFT)14 was used. The Becke three-parameter exchange functional and the nonlocal correlation functional of Lee, Yang, and Parr (B3LYP) with the 6-31G* set for C, H, Zn, O, Cl, and P, in conjunction with the Stuttgart/Dresden relativistic effective core potentials for Pd, were used to compute the geometries, energies, and normal-mode vibration frequencies of the starting material, the corresponding transition structures, and the products. We have recalculated some of the structures, namely the transformation IVa → TSVa → Va, as single-point calculations with a 6-311G*/SDD basis set to further validate the results and found very minor differences (less than 0.2 kcal/mol) with a threefold more expensive cost-on CPU time. The stationary points were charact
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Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Montgomery, J. A, Jr, Vreven, T, Kudin, K. N, Burant, J. C, Millam, J. M, Iyengar, S. S, Tomasi, J, Barone, V, Mennucci, B, Cossi, M, Scalmani, G, Rega, N, Petersson, G. A, Nakatsuji, H, Hada, M, Ehara, M, Toyota, K, Fukuda, R, Hasegawa, J, Ishida, M, Nakajima, T, Honda, Y, Kitao, O, Nakai, H, Klene, M, Li, X, Knox, J. E, Hratchian, H. P, Cross, J. B, Bakken, V, Adamo, C, Jaramillo, J, Gomperts, R, Stratmann, R. E, Yazyev, O, Austin, A. J, Cammi, R, Pomelli, C, Ochterski, J. W, Ayala, P. Y, Morokuma, K, Voth, G. A, Salvador, P, Dannenberg, J. J, Zakrzewski, V. G, Dapprich, S, Daniels, A. D, Strain, M. C, Farkas, O, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Ortiz, J. V, Cui, Q, Baboul, A. G, Clifford, S, Cioslowski, J, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Martin, R. L, Fox, D. J, Keit
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Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.
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For an overview of alloyed Pd-Zn bimetallic catalysts, see
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For an overview of alloyed Pd-Zn bimetallic catalysts, see: Coq, B.; Figueras, F. J. Mol. Catal. A 2001, 173, 117-134.
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Figueras, F.2
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sp ring that participates in an oxidative-addition-Sn-migration step. This pathway, which appears to be a minor one in that Pd-catalyzed reaction, is however the most favorable one when Pt replaces Pd in the calculations. See: Matsubara, T. Organometallics 2003, 22, 4297-4304.
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sp ring that participates in an oxidative-addition-Sn-migration step. This pathway, which appears to be a minor one in that Pd-catalyzed reaction, is however the most favorable one when Pt replaces Pd in the calculations. See: Matsubara, T. Organometallics 2003, 22, 4297-4304.
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33645383779
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The X-ray structure of EtZnCl displays tetrahedral Zn atoms coordinated to one ethyl and three chloride ligands: Guerrero, A, Hughes, D. L, Bochmann, M. Organometallics 2006, 25, 1525-1527
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The X-ray structure of EtZnCl displays tetrahedral Zn atoms coordinated to one ethyl and three chloride ligands: Guerrero, A.; Hughes, D. L.; Bochmann, M. Organometallics 2006, 25, 1525-1527.
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37
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2Zn and Ni(0) has been similarly suggested, on the basis of DFT calculations, to lead to the formation of a bimetallic Ni-C-Zn three-membered ring with a Ni-Zn bond and a bridging methyl group: Hratchian, H. P.; Chowdhury, S. K.; Gutiérrez-García, V. M.; Amarasinghe, K. K. D.; Heeg, M. J.; Schlegel, H. B.; Montgomery, J. Organometallics 2004, 23, 4636-4646.
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2Zn and Ni(0) has been similarly suggested, on the basis of DFT calculations, to lead to the formation of a bimetallic Ni-C-Zn three-membered ring with a Ni-Zn bond and a bridging methyl group: Hratchian, H. P.; Chowdhury, S. K.; Gutiérrez-García, V. M.; Amarasinghe, K. K. D.; Heeg, M. J.; Schlegel, H. B.; Montgomery, J. Organometallics 2004, 23, 4636-4646.
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2 appears to be a multistep process, which is presently under study.
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2 appears to be a multistep process, which is presently under study.
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With IIIa as an example, the Zn-Cl and Pd-Cl distances are 2.43 and 2.50 A, respectively. In comparison. X-ray diffraction data of a new dinuclear palladium complex bridged by a chlorine atom have been recently reported with Pd-Cl distances of 2.44 Å (for the Cl-PdCl-[Pd] bond) and 2.35 Å (for the ArP-Pd-Cl-[Pd] bond): Christmann, U.; Pantazis, D. A.; Benet-Buchholz, J.; McGrady, J. E.; Maseras, F.; Vilar, R. J. Am. Chem. Soc. 2006, 128, 6376-6390.
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With IIIa as an example, the Zn-Cl and Pd-Cl distances are 2.43 and 2.50 A, respectively. In comparison. X-ray diffraction data of a new dinuclear palladium complex bridged by a chlorine atom have been recently reported with Pd-Cl distances of 2.44 Å (for the Cl-PdCl-[Pd] bond) and 2.35 Å (for the ArP-Pd-Cl-[Pd] bond): Christmann, U.; Pantazis, D. A.; Benet-Buchholz, J.; McGrady, J. E.; Maseras, F.; Vilar, R. J. Am. Chem. Soc. 2006, 128, 6376-6390.
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The pathways starting from Ia and Ib converge at IIIa, implying displacement of a solvent molecule from complex IIb. Alternatively, a phosphine ligand could be displaced from a diastereoisomeric form of IIb but this pathway has a much higher activation energy (20.49 kcal/mol).
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The pathways starting from Ia and Ib converge at IIIa, implying displacement of a solvent molecule from complex IIb. Alternatively, a phosphine ligand could be displaced from a diastereoisomeric form of IIb but this pathway has a much higher activation energy (20.49 kcal/mol).
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The transition states TSIIIa and TSIIb-IIIa connecting II to III (confirmed with a relaxed scans calculation along the reaction coordinates) are characterized by motions associated with the imaginary frequency that reflect the weakening of the Pd-P and Zn-Cl bonds as well as the incipient formation of a Pd-Cl bond. However, we were unable to locate the corresponding transition structure for the transformation IIc to IIIc.
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The transition states TSIIIa and TSIIb-IIIa connecting II to III (confirmed with a relaxed scans calculation along the reaction coordinates) are characterized by motions associated with the imaginary frequency that reflect the weakening of the Pd-P and Zn-Cl bonds as well as the incipient formation of a Pd-Cl bond. However, we were unable to locate the corresponding transition structure for the transformation IIc to IIIc.
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Interestingly, a recent paper reported the X-ray crystal structure of a Ni-Al dinuclear complex with a bridging methyl group which would also be a model for a transmetalation event: Ogoshi, S.; Ueta, M.; Arai, T.; Kurosawa, H. J. Am. Chem. Soc. 2005, 127, 12810-12811.
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Interestingly, a recent paper reported the X-ray crystal structure of a Ni-Al dinuclear complex with a bridging methyl group which would also be a model for a transmetalation event: Ogoshi, S.; Ueta, M.; Arai, T.; Kurosawa, H. J. Am. Chem. Soc. 2005, 127, 12810-12811.
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Pd and Zn, in their respective conversions into the square-planar and tetrahedral geometries present in the resulting allenylzinc
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The imaginary frequency associated with the late transition state TSIVa (which was validated by a a relaxed scans calculation along the reaction coordinates) shows the geometric changes occurring at both metal centers
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The imaginary frequency associated with the late transition state TSIVa (which was validated by a a relaxed scans calculation along the reaction coordinates) shows the geometric changes occurring at both metal centers, Pd and Zn, in their respective conversions into the square-planar and tetrahedral geometries present in the resulting allenylzinc IVa.
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IVa
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For a synergistic effect between Pd and other metals in cross-couplings with mixed-metal catalysts, see:, and references cited therein
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For a synergistic effect between Pd and other metals in cross-couplings with mixed-metal catalysts, see: Shenglof, M.; Molander, G. A.; Blum, J. Synthesis 2006, 111-114 and references cited therein.
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Shenglof, M.1
Molander, G.A.2
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See also: Adams, R. D.; Captain, B.; Zhu, L. J. Am. Chem. Soc. 2006, 128, 13672-13673.
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Adams, R.D.1
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