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DZP refers to the standard DZP basis sets for C, N, and H atoms and the pseudopotential-including basis set Lanl2dz for Cu. Geometric optimizations were performed without any constraints. A scaling factor of 0.9804 was used for computing thermal energy corrections within B3LYP/6-31G*. The relative electron energy [ΔG = G(1b) - G(1a)] and entropy [ΔS = S(1b) - S(1a)] at different temperatures were calculated at the B3LYP/DZP level of theory: T = 100, 150, 195, 200, 300 K, ΔG = 0.53, 0.25, 0.00, -0.04, -0.61 kcal/mol, and ΔS = 5.63, 5.70, 5.73, 5.74, 5.77 cal/molK, respectively. By extrapolation, 1a was computed to be ca. 1.15 kcal/mol lower in energy than 1b at 0 K. All computations were performed with the Gaussian 03 package of programs: c) M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery Jr., T. Vreven, K. N, Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O, Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian 03, revision C.02, Gaussian, Inc., Wallingford, CT, 2004.
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