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Volumn 46, Issue 4, 2007, Pages 1488-1501

Structure and bonding of vanadium(V) complexes with hydroxyurea in aqueous solution: Density functional theory investigations of isomers and intramolecular rearrangements

Author keywords

[No Author keywords available]

Indexed keywords

HYDROXYUREA; LIGAND; ORGANOMETALLIC COMPOUND; PROTON; VANADIUM; WATER;

EID: 33847742649     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic061699y     Document Type: Article
Times cited : (8)

References (78)
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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.; Salvafdor, 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; Gaussian, Inc.: Wallingford, CT, 2004.
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    • CPMD Version 3.7.0; Copyright IBM Corp. 1990-2001, Copyright MPI für Festkörperforschung Stuttgart 1997-2001
    • CPMD Version 3.7.0; Copyright IBM Corp. 1990-2001, Copyright MPI für Festkörperforschung Stuttgart 1997-2001.
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    • The notations AE1 and CP-opt thus denote two different approximations for constructing the Kohn-Sham wavefunction, namely one based on an all-electron basis set moving with the atoms and the other on atomic pseudopotential cores swimming in a sea of periodic planewaves.
    • The notations AE1 and CP-opt thus denote two different approximations for constructing the Kohn-Sham wavefunction, namely one based on an all-electron basis set moving with the atoms and the other on atomic pseudopotential cores swimming in a sea of periodic planewaves.
  • 43
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    • Equatorial and axial denote positions with respect to the idealized plane formed by the V-O-C-N-O chelate ring
    • Equatorial and axial denote positions with respect to the idealized plane formed by the V-O-C-N-O chelate ring.
  • 55
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    • 2O should be thermoneutral in water, as it just describes the exchange of one solvent molecule from the second hydration sphere with one from the bulk. In contrast, the PCM data in Table 5 would a predict a driving force of as much as +8.8 kcal/mol for this process.
    • 2O should be thermoneutral in water, as it just describes the exchange of one solvent molecule from the second hydration sphere with one from the bulk. In contrast, the PCM data in Table 5 would a predict a driving force of as much as +8.8 kcal/mol for this process.
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    • The standard Gibbs free energy of each species in the gas phase in its standard state (ideal gas at 1 atm and 298 K) is obtained by the following equation: ΔG0g, E0K, ZPE, ΔΔG0→298K. The total energy of the molecule at 0 K (E0K) is calculated at the optimum geometry from BP86. The zero-point energy (ZPE) and the Gibbs free energy change from 0 to 298 K at 1 atm (ΔΔG0→298K) are calculated from the vibrational frequencies using BP86. Translational and rotational free energy contribution is also calculated in the ideal gas approximation. The standard free energy of solvation in water [e.g. ΔG 0(2aq) and ΔG 01aq, was calculated as a difference between the SCF energies from gas phase and solvated calculations. To obtain ΔG0aq,deprotonat
    • g (1 atm) + RT ln(24.46).
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    • There is evidence that gradient-corrected functionals such as BP86 tend to underestimate binding energies of water ligands with transition-metal-aquo complexes, cf.: Rotzinger, F. R. J. Phys. Chem. B 2005, 109, 1510-1527.
    • There is evidence that gradient-corrected functionals such as BP86 tend to underestimate binding energies of water ligands with transition-metal-aquo complexes, cf.: Rotzinger, F. R. J. Phys. Chem. B 2005, 109, 1510-1527.
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    • Single-point energy computations at the B3LYP/AE1 level afford somewhat higher barriers compared to the BP86 data (a typical effect of including Hartree-Fock exchange in the exchange-correlation functional). Even though this difference in computed barrier heights can approach ca. 8 kcal/mol in individual cases (see data in Table S5 of the Supporting Information), the qualitative conclusions (in particular concerning solvent assistance) are not affected.
    • Single-point energy computations at the B3LYP/AE1 level afford somewhat higher barriers compared to the BP86 data (a typical effect of including Hartree-Fock exchange in the exchange-correlation functional). Even though this difference in computed barrier heights can approach ca. 8 kcal/mol in individual cases (see data in Table S5 of the Supporting Information), the qualitative conclusions (in particular concerning solvent assistance) are not affected.
  • 78


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