Bergman, Aza-Bergman, and protonated Aza-Bergman cyclizations and intermediate 2,5-arynes: Chemistry and challenges to computation

Journal of the American Chemical Society

Volumn 120, Issue 25, 1998, Pages 6261-6269

  Cramer, Christopher J ^a  

^a Department of Chemistry Supercomputer Institute ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANTINEOPLASTIC ACTIVITY; ARTICLE; CYCLIZATION; CYTOTOXICITY; MOLECULAR INTERACTION; PROTON TRANSPORT;

EID: 0032125865     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9806579     Document Type: Article

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100. I have also surveyed the QCISD(T) method (Pople, J. A.; Head-Gordon, M.; Raghavachari, K. J. Chem. Phys. 1987, 87, 5968) for these systems. It appears to be much less unstable than CCSD(T), giving relative energies within 1 kcal/mol of the BCCD(T) results. This is somewhat surprising, since the single excitation amplitudes in the QCISD(T) calculations are even larger than those for the CCSD(T) calculations. Given this potential for instability, and given other criticisms of QCISD(T) theory relative to CCSD(T) or BCCD(T) (Scuseria, G. E.; Schaefer, H. F., III J. Chem. Phys. 1989, 90, 3700; Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M. Chem. Phys. Lett. 1989, 157, 479. Lee, T. J.; Rendell, A. P.; Taylor, P. R. J. Phys. Chem. 1990, 94, 5463. He, Z.; Cremer, D. Theor. Chim. Acta 1993, 85, 305), I consider BCCD(T) to be the best choice in low-symmetry aryne systems where large single excitation amplitudes are observed with HF orbitals. However, further studies germane to this point are warranted.
101. I have also surveyed the QCISD(T) method (Pople, J. A.; Head-Gordon, M.; Raghavachari, K. J. Chem. Phys. 1987, 87, 5968) for these systems. It appears to be much less unstable than CCSD(T), giving relative energies within 1 kcal/mol of the BCCD(T) results. This is somewhat surprising, since the single excitation amplitudes in the QCISD(T) calculations are even larger than those for the CCSD(T) calculations. Given this potential for instability, and given other criticisms of QCISD(T) theory relative to CCSD(T) or BCCD(T) (Scuseria, G. E.; Schaefer, H. F., III J. Chem. Phys. 1989, 90, 3700; Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M. Chem. Phys. Lett. 1989, 157, 479. Lee, T. J.; Rendell, A. P.; Taylor, P. R. J. Phys. Chem. 1990, 94, 5463. He, Z.; Cremer, D. Theor. Chim. Acta 1993, 85, 305), I consider BCCD(T) to be the best choice in low-symmetry aryne systems where large single excitation amplitudes are observed with HF orbitals. However, further studies germane to this point are warranted.
102. I have also surveyed the QCISD(T) method (Pople, J. A.; Head-Gordon, M.; Raghavachari, K. J. Chem. Phys. 1987, 87, 5968) for these systems. It appears to be much less unstable than CCSD(T), giving relative energies within 1 kcal/mol of the BCCD(T) results. This is somewhat surprising, since the single excitation amplitudes in the QCISD(T) calculations are even larger than those for the CCSD(T) calculations. Given this potential for instability, and given other criticisms of QCISD(T) theory relative to CCSD(T) or BCCD(T) (Scuseria, G. E.; Schaefer, H. F., III J. Chem. Phys. 1989, 90, 3700; Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M. Chem. Phys. Lett. 1989, 157, 479. Lee, T. J.; Rendell, A. P.; Taylor, P. R. J. Phys. Chem. 1990, 94, 5463. He, Z.; Cremer, D. Theor. Chim. Acta 1993, 85, 305), I consider BCCD(T) to be the best choice in low-symmetry aryne systems where large single excitation amplitudes are observed with HF orbitals. However, further studies germane to this point are warranted.
103. I have also surveyed the QCISD(T) method (Pople, J. A.; Head-Gordon, M.; Raghavachari, K. J. Chem. Phys. 1987, 87, 5968) for these systems. It appears to be much less unstable than CCSD(T), giving relative energies within 1 kcal/mol of the BCCD(T) results. This is somewhat surprising, since the single excitation amplitudes in the QCISD(T) calculations are even larger than those for the CCSD(T) calculations. Given this potential for instability, and given other criticisms of QCISD(T) theory relative to CCSD(T) or BCCD(T) (Scuseria, G. E.; Schaefer, H. F., III J. Chem. Phys. 1989, 90, 3700; Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M. Chem. Phys. Lett. 1989, 157, 479. Lee, T. J.; Rendell, A. P.; Taylor, P. R. J. Phys. Chem. 1990, 94, 5463. He, Z.; Cremer, D. Theor. Chim. Acta 1993, 85, 305), I consider BCCD(T) to be the best choice in low-symmetry aryne systems where large single excitation amplitudes are observed with HF orbitals. However, further studies germane to this point are warranted.
104. I have also surveyed the QCISD(T) method (Pople, J. A.; Head-Gordon, M.; Raghavachari, K. J. Chem. Phys. 1987, 87, 5968) for these systems. It appears to be much less unstable than CCSD(T), giving relative energies within 1 kcal/mol of the BCCD(T) results. This is somewhat surprising, since the single excitation amplitudes in the QCISD(T) calculations are even larger than those for the CCSD(T) calculations. Given this potential for instability, and given other criticisms of QCISD(T) theory relative to CCSD(T) or BCCD(T) (Scuseria, G. E.; Schaefer, H. F., III J. Chem. Phys. 1989, 90, 3700; Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M. Chem. Phys. Lett. 1989, 157, 479. Lee, T. J.; Rendell, A. P.; Taylor, P. R. J. Phys. Chem. 1990, 94, 5463. He, Z.; Cremer, D. Theor. Chim. Acta 1993, 85, 305), I consider BCCD(T) to be the best choice in low-symmetry aryne systems where large single excitation amplitudes are observed with HF orbitals. However, further studies germane to this point are warranted.
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