[en] Density functional theory has been used to study the electronic spin-state properties of low-spin Fe[HB(PZ)(3)](2), lhigh-spin Fe[HB(3-MePZ)(3)](2), high-spin Fe[HB(3,5-Me(2)PZ)(3)](2), and high-spin Fe[HB(3,4,5-Me(3)PZ)(3)](2) complexes that exhibit very different iron(II) electronic spin-sate crossover behaviors with changing temperature and pressure. Excellent agreement is obtained between the experimentally,observed Mossbauer-effect quadrupole splittings and isomer shifts of these complexes and those calculated with the B3LYP functional and various different basis sets for both the high-spin and low-spin states of iron(II). The calculations for Fe[HB(PZ)(3)](2) that use the LANL2DZ, 6-31++G(d,p), and 6-311++G(d,p) basis sets for iron all lead to very similar electric field gradients and thus quadrupole splittings. The initial calculations, which were based upon the known X-ray structures, were followed by structural optimization, an optimization that led to small increases in the Fe-N bond distances. Optimization led to at most trivial changes in the intraligand bond distances and angles. The importance of the 3-methy I-H center dot center dot center dot H-3-methyl nonbonded intramolecular interligand interactions in controlling the minimum Fe-N bond distances and determining the iron(II) spin state both in Fe[HB(3-Mepz)(3)](2) and in the related methyl-substituted complexes has been identified.
Disciplines :
Chemistry
Author, co-author :
Remacle, Françoise ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Long, G. J.
Grandjean, Fernande ; Université de Liège - ULiège > Département de physique > Département de physique
Language :
English
Title :
A density functional theory calculation of the electronic properties of several high-spin and low-spin iron(II) pyrazolylborate complexes
Publication date :
2008
Journal title :
Inorganic Chemistry
ISSN :
0020-1669
eISSN :
1520-510X
Publisher :
American Chemical Society, Washington, United States - District of Columbia
Gütlich, P., Goodwin, H. A., Eds. Spin Crossover in Transition Metal Compounds I-III; Springer-Verlag: Berlin, Germany, 2004.
Reger, D. L.; Gardinier, J. R.; Elgin, J. D.; Smith, M. D.; Hautot, D.; Long, G. J.; Grandjean, F. Inorg. Chem. 2006, 45, 8862-8875.
Ingalls, R. Phys. Rev. 1964, 133A, 787-795.
DeBenedetti, S.; Lang, G.; Ingalls, R. Phys. Rev. Lett. 1961, 6, 60-62.
Danon, J. In Chemical Applications of Mössbauer Spectroscopy; Goldanskii, V. I., Herber, R. H., Eds.; Academic Press: New York, 1968; pp 159-267.
Gütlich, P. In Mössbauer Spectroscopy; Gonser, U., Ed.; Springer-Verlag: Berlin, Germany, 1975; pp 53-96.
Trofimenko, S. Scorpionates: The Coordination Chemistry of Polypyrazolylborate Ligands; Imperial College Press: London, 1999.
Jesson, J. P.; Trofimenko, S.; Eaton, D. R. J. Am. Chem. Soc. 1967, 89, 3158-3164.
Jesson, J. P.; Weiher, J. F.; Trofimenko, S. J. Chem. Phys. 1968, 48, 2058-2066.
Trofimenko, S. Chem. Rev. 1993, 93, 943-980.
Long, G. J.; Grandjean, F.; Reger, D. L. In Spin Crossover in Transition Metal Compounds I; Gütlich, P., Goodwin, H. A., Eds.; Springer-Verlag: Berlin, Germany, 2004; p 93.
Long, G. J.; Hutchinson, B. B. Inorg. Chem. 1987, 26, 608-613.
Grandjean, F.; Long, G. J.; Hutchinson, B. B.; Ohlhausen, L.; Neill, P.; Holcomb, J. D. Inorg. Chem. 1989, 28, 4406-4414.
Oliver, J. D.; Mullica, D. F.; Hutchinson, B. B.; Milligan, W. O. Inorg. Chem. 1980, 19, 165-169.
Havlin, R. H.; Godbout, N.; Salzmann, R.; Wojdelski, M.; Arnold, W.; Schultz, C. E.; Oldfield, E. J. Am. Chem. Soc. 1998, 120, 3144-3151.
Godbout, N.; Havlin, R. H.; Salzmann, R.; Debrunner, P. G.; Oldfield, E. J. Phys. Chem. A 1998, 102, 2342-2350.
Zhang, Y.; Oldfield, E. J. Phys. Chem. A 2003, 107, 4147-4150.
Zhang, Y.; Mao, J.; Oldfield, E. J. Am. Chem. Soc. 2002, 124, 7829-7839.
Paulsen, H.; Trautwein, A. X. J. Phys. Chem. Solids 2004, 65, 793-798.
Paulsen, H.; Trautwein, A. X. In Spin Crossover in Transition Metal Compounds III; Gütlich, P., Goodwin, H. A., Eds.; Springer-Verlag: Berlin, Germany, 2004; p 197.
Reger, D. L.; Little, C. A.; Rheingold, A. L.; Lam, M.; Liable-Sands, M.; Rhagitan, B.; Concolino, T.; Mohan, A.; Long, G. J.; Briois, V.; Grandjean, F. Inorg. Chem. 2001, 40, 1508-1520.
Reger, D. L.; Little, C. A.; Smith, M. D.; Rheingold, A. L.; Lam, K.-C.; Concolino, T. L.; Long, G. J.; Hermann, R. P.; Grandjean, F. Eur. J. Inorg. Chem. 2002, 1190-1197.
Reger, D. L.; Gardinier, J. R.; Bakbak, S.; Gemmill, W.; Smith, M. D.; Rebbouh, L.; Grandjean, F.; Shahin, A. M.; Long, G. J. J. Am. Chem. Soc. 2005, 127, 2303-2316.
Reger, D. L.; Gardinier, J. R.; Smith, M. D.; Shahin, A. M.; Long, G. J.; Rebbouh, L.; Grandjean, F. Inorg. Chem. 2005, 44, 1852-1866.
Frisch, M. J.; Tracks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millan, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Peterson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian03, revision B.1; Gaussian Inc.:, Pittsburgh, PA, 2003.
Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 270-283.
1985, 82, 299-310.
Schwerdtfeger, P.; Söhnel, T.; Pempointner, M.; Laerdahl, J. K.; Wagner, F. E. J. Chem. Phys. 2001, 115, 5913-5924.
Engel, T. Quantum Chemistry and Spectroscopy; Pearson-Benjamin Cummings: San Francisco, CA, 2006.
Neese, F. J. Biol. Inorg. Chem. 2006, 11, 702-711.
Berry, J. F.; Bill, E.; Bothe, E.; George, S. D.; Mienert, B.; Neese, F.; Wieghardt, K. Science 2006, 312, 1937-1941.
Wang, H.; Xie, Y.; King, R. B.; Schaefer, H. F., III J. Am. Chem. Soc. 2005, 127, 11646-11651.
Wang, H.; Xie, Y.; King, R. B.; Schaefer, H. F., III J. Am. Chem. Soc. 2006, 128, 11376-11384.
Carpenter, J. E.; Weinhold, F. THEOCHEM 1988, 46, 41-62.
Barone, V. Chem. Phys. Lett. 1996, 262, 201-206.
Neese, F. Inorg. Chim. Acta 2002, 337, 181-192.
Neese, F.; Wolf, A.; Fleig, T.; Reiher, M.; Hesse, B. A. J. Chem. Phys. 2005, 122, 204107. (10 pages) and references cited therein.
Freemann, A. J.; Ellis, D. E. In Mössbauer Isomer Shifts; Shenoy, G. K., Wagner, F. E., Eds.; North-Holland: Amsterdam, The Netherlands, 1978; pp 111-201.
Manoharan, P. T.; Hamilton, W. C. Inorg. Chem. 1963, 2, 1043-1047.
Zein, S.; Matouzenko, G. S.; Borshch, S. A. Chem. Phys. Lett. 2004, 397, 475-478.
Neese, F. Curr. Opin. Chem. Biol. 2003, 7, 125-135.
Cramer, C. J. Essentials of Computational Chemistry; Wiley: Chichester, U.K., 2003.
Ratner, M. A.; Schatz, G. C. Introduction to Quantum Mechanics in Chemistry; Prentice-Hall: New York, 2001.
Wachters, A. J. H. J. Chem. Phys. 1970, 52, 1033-1036.
Hay, P. J. J. Chem. Phys. 1977, 66, 4377-4384.
Frisch, A.; Dennington, R. D.; Nielsen, A. B.; Holder, A. J. GaussView Reference; Gaussian, Inc.: Carnegie, PA, 2003.
Dufek, P.; Blaha, P.; Schwarz, K. Phys. Rev. Lett. 1995, 75, 3545-3548.
Wolny, J. A.; Paulsen, H.; Winkler, H.; Trautwein, A. X.; Tuchagues, J. P. Hyperfine Interact. 2005, 166, 495-498.
Böttger, L. H.; Chumakov, A. I.; Grunert, C. M.; Gütlich, P.; Kusz, J.; Paulsen, H.; Ponkratz, U.; Rusanov, V.; Trautwein, A. X.; Wolny, J. A. Chem. Phys. Lett. 2006, 429, 189-193.
Stevens, J. G.; Stevens, V. E. Mössbauer Effect Data Index; Plenum: New York, 2006; p 62.
Shenoy, G. K.; Wagner, F. E.; Kalvius, G. M. In Mössbauer Isomer Shifts; Shenoy, G. K., Wagner, F. E., Eds.; North-Holland: Amsterdam, The Netherlands, 1978; pp 49-110.
Nieuwpoort, W. C.; Post, D.; Van Duinen, P. Th. Phys. Rev. B 1978, 17, 91-98.