E. Anders et al.
FULL PAPER
[10]
[11]
[12]
[13]
S. Blezinger, C. Wilhelm, J. Kesselmeier, Biogeochemistry 2000,
48, 185–197.
U. Kuhn, A. Wolf, C. Gries, T. H. Nash, J. Kesselmeier, Atmos.
Environ. 2000, 34, 4867–4878.
J. Kesselmeier, A. Hubert, Atmos. Environ. 2002, 36, 4679–
4686.
M. Bräuer, E. Anders, S. Sinnecker, W. Koch, M. Rombach,
H. Brombacher, H. Vahrenkamp, Chem. Commun. 2000, 647–
648.
S. Sinnecker, M. Bräuer, W. Koch, E. Anders, Inorg. Chem.
2001, 40, 1006–1013.
charges distributed on the cavity surface. This procedure is known
to be very good at reproducing experimental hydration energies.[30]
In the framework of the C-PCM model the default UA0 cavities
(based on the united atom topological model) and the dielectric
constant of chloroform (ε = 4.9) were used.
For all single point calculations the B98[33] functional was used.
The G3MP2Large basis set[34] was employed on all atoms except
zinc where the 6-311+G(3df) basis set as implemented in
Gaussian03 was applied. The B98 density functional was chosen
for the calculation of the energies because it has recently been
shown that it outperforms the more popular B3LYP functional,
both for absolute energies and barrier heights, especially for larger
molecules.[35–37] In all these studies the assessment was performed
using single point calculations on some reference geometry, basi-
cally the same approach that we used in this work. We therefore
believe that the use of the well-established B3LYP density func-
tional for the geometry optimizations has only a minor effect on
the calculated energies. This is even more plausible with respect to
the fact that geometry relaxation effects from the dielectric field of
the solvent are completely neglected. The absolute error of B98 on
the G3/05 set is approximately 14 kJ·mol–1,[35] but the relative er-
rors are generally smaller.
[14]
[15]
[16]
[17]
[18]
M. Rombach, H. Vahrenkamp, Inorg. Chem. 2001, 40, 6144–
6150.
R. Luckay, T. E. Chantson, J. H. Reibenspies, R. D. Hancock,
J. Chem. Soc., Dalton Trans. 1995, 1363–1367.
F. Wagner, M. T. Mocella, M. J. D’Aniello Jr, A. H.-J. Wang,
E. K. Barefield, J. Am. Chem. Soc. 1974, 96, 2625–2627.
D. Schröder, H. Schwarz, S. Schenk, E. Anders, Angew. Chem.
Int. Ed. 2003, 42, 5087–5090; Angew. Chem. 2003, 115, 5241–
5244.
A. Bottoni, C. Z. Lanza, G. P. Miscione, D. Spinelli, J. Am.
Chem. Soc. 2004, 126, 1542–1550.
Molen, an interactive structure solution procedure, 1999, Enraf–
Nonius, Delft, The Netherlands.
[19]
[20]
[21]
[22]
[23]
[24]
Collect, data collection software, 1998, Nonius, The Nether-
lands.
G. M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr.
1990, 46, 467–473.
All energies were calculated by adding the appropriate thermo-
dynamic corrections [gas phase, B3LYP/6-311+G(d)] to the total
free energy in solution (including electrostatic and nonelectrostatic
terms) obtained from the single point calculations (B98/
G3MP2Large). The gas phase correction values were calculated
with the standard thermodynamic routines in Gaussian03 (with T
= 298.15 K and p = 1 atm) using the frequencies computed at the
B3LYP/6-311+G(d) optimal gas phase geometries.
G. M. Sheldrick, Shelxl-97, release 97-2, 1997, University of
A. L. Spek, Platon, a multipurpose crystallographic tool, 2004,
Utrecht University, Utrecht, The Netherlands, http://
www.cryst.chem.uu.nl/platon.
CCDC-258933 (for 1a) and -286778 (for 2a) contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
S. Tanimoto, T. Oida, H. Ikehira, M. Okano, Bull. Chem. Soc.
Jpn. 1982, 55, 1977–1978.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, J. A. J. A. Montgomery Jr,
T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyen-
gar, 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, C. Adamo, J. Jaramillo, R. Gom-
perts, 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. Dap-
prich, 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. Nanayak-
kara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen,
M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian03, revision
C.02, 2004, Gaussian, Inc., Wallingford, CT, http://www.gaus-
sian.com.
[25]
Supporting Information (see footnote on the first page of this arti-
cle): Details are given on the Raman spectroscopy (including two
spectra), the solid-state NMR spectroscopy (including four spec-
tra), and the analysis of the kinetic data (including two kinetic
plots). The Cartesian coordinates and absolute energies of all calcu-
lated structures are provided.
[26]
[27]
Acknowledgments
Financial support of this work by the Deutsche Forschungsgemein-
schaft, SFB 436 “Metal Mediated Reactions Modeled After Na-
ture” is gratefully acknowledged.
[1] J. Notni, H. Görls, E. Anders, Eur. J. Inorg. Chem. 2006, 1444–
1455.
[2] G. Parkin, Chem. Rev. (Washington, DC, U. S.) 2004, 104,
699–767.
[3] F. Botre, G. Gros, B. T. Storey, Carbonic Anhydrase, VCH, New
York, 1991.
[4] I. Bertini, C. Luchinat, W. Maret, M. Zeppezauer, Zinc En-
zymes, Birkhäuser, Boston, 1986.
[28]
[29]
A. D. Becke, J. Chem. Phys. 1993, 98, 5648–5652.
C. Lee, W. Yang, R. G. Parr, Phys. Rev. B: Condens. Matter
Mater. Phys. 1988, 37, 785–789.
V. Barone, M. Cossi, J. Phys. Chem. A 1998, 102, 1995–2001.
M. Cossi, N. Rega, G. Scalmani, V. Barone, J. Comput. Chem.
2003, 24, 669–681.
A. Klamt, G. Schüürmann, J. Chem. Soc., Perkin Trans. 2 1993,
799–805.
H. L. Schmider, A. D. Becke, J. Chem. Phys. 1998, 108, 9624–
9631.
[5] S. Schenk, J. Kesselmeier, E. Anders, Chem. Eur. J. 2004, 10,
3091–3105.
[6] M. Mauksch, M. Bräuer, J. Weston, E. Anders, ChemBioChem
2001, 2, 190–198.
[7] M. Bräuer, J. L. Pérez-Lustres, J. Weston, E. Anders, Inorg.
Chem. 2002, 41, 1454–1463.
[8] U. Kuhn, C. Ammann, A. Wolf, F. X. Meixner, M. O. Andreae,
J. Kesselmeier, Atmos. Environ. 1999, 33, 995–1008.
[9] G. Protoschill-Krebs, C. Wilhelm, J. Kesselmeier, Atmos. Envi-
ron. 1996, 30, 3151–3156.
[30]
[31]
[32]
[33]
2790
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 2783–2791