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Not innocent : verdict from ab initio multiconfigurational second-order perturbation theory on the electronic structure of chloroiron corrole
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Roos, Bjorn O., Veryazov, Valera, Conradie, Jeanet, Taylor, Peter R. (Peter Robert) and Ghosh, Abhik. (2008) Not innocent : verdict from ab initio multiconfigurational second-order perturbation theory on the electronic structure of chloroiron corrole. The Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical, Vol.112 (No.45). pp. 14099-14102. ISSN 1520-6106
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Official URL: http://dx.doi.org/10.1021/jp807734x
Abstract
From a suitably broad perspective, transition metal corroles may be viewed as stable, synthetic analogues of high-valent heme protein intermediates such as compounds I and II. Against this backdrop, the electronic structure of chloroiron corrole has provoked a lively debate in recent years. Thus, whereas NMR spectroscopy and DFT calculations suggest an S = 3/2 Fe(III) corrole(center dot 2-) radical description, certain researchers have favored an Fe(IV) formulation. These two descriptions are indistinguishable as far as DFT calculations are concerned. Ab initio CASSCF/CASPT2 calculations provide unambiguous support for the former description. In addition, they rule out any Fe(IV) state, whether high- or low-spin, within 1.5 eV of the ground state.
| Item Type: | Journal Article |
|---|---|
| Subjects: | Q Science > QA Mathematics Q Science > QD Chemistry |
| Divisions: | Faculty of Science > Chemistry |
| Library of Congress Subject Headings (LCSH): | Perturbation (Mathematics), Density functionals |
| Journal or Publication Title: | The Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical |
| Publisher: | American Chemical Society |
| ISSN: | 1520-6106 |
| Date: | 13 November 2008 |
| Volume: | Vol.112 |
| Number: | No.45 |
| Number of Pages: | 4 |
| Page Range: | pp. 14099-14102 |
| Identification Number: | 10.1021/jp807734x |
| Status: | Peer Reviewed |
| Publication Status: | Published |
| Access rights to Published version: | Restricted or Subscription Access |
| Funder: | Royal Society (Great Britain), Norges forskningsråd [Norwegian Research Council], Sweden. Vetenskapsrådet [Swedish Research Council], Wolfson Foundation |
| References: | (1) For reviews, see: (a) Walker, F. A.; Licoccia, S.; Paolesse, R. J. Inorg. Biochem. 2006, 100, 810–837. (b) Gross, Z.; Gray, H. B. Comments Inorg. Chem. 2006, 27, 61–72. (2) (a) Cai, S.; Walker, F. A.; Licoccia, S. Inorg. Chem. 2000, 39, 3466–3478. (b) Zakharieva, O.; Schunemann, V.; Gerdan, M.; Licoccia, S.; Cai, S.; Walker, F. A.; Trautwein, A. X. J. Am. Chem. Soc. 2002, 124, 6636–6648. (3) (a) Steene, E.; Wondimagegn, T.; Ghosh, A. J. Phys. Chem. B 2001, 105, 11406–11413; addition/correction: J. Phys. Chem. B 2002, 106, 5312- 5312. (b) Steene, E.; Wondimagegn, T.; Ghosh, A. J. Am. Chem. Soc. 2003, 125, 16300–16309. (4) Ahlrichs, R.; Bar, M.; Haser, M.; Horn, H.; Kolmel, C. Chem. Phys. Lett. 1989, 162, 165–169. (5) Karlstro¨m, G.; Lindh, R.; Malmqvist, P.-Å.; Roos, B. O.; Ryde, U.; Veryazov, V.; Widmark, P.-O.; Cossi, M.; Schimmelpfennig, B.; Neogrady, P.; Seijo, L. Comput. Mater. Sci. 2003, 28, 222. (6) Aquilante, F.; Malmqvist, P.-Å.; Pedersen, T. B.; Ghosh, A.; Roos, B. O. J. Chem. Theory Comput. 2008, 4, 694–702. (7) Roos, B. O.; Lindh, R.; Malmqvist, P.-Å.; Veryazov, V.; Widmark, P.-O. J. Phys. Chem. A 2005, 109, 6575. Hess, B. A. Phys. ReV. 1986, A33, 3742–3748. (9) Roos, B. O.; Andersson, K.; Fu¨lscher; M. P.; Malmqvist, P.-Å.; Serrano-Andres, L.; Pierloot, K.; Merchan, M. AdV. Chem. Phys. 1996, 93, 219–331. (10) An S ) 2 ground-state has been reported for a saddled, undecasubstituted Fe(Cor)Cl derivative. We speculate that the reduced out-of-plane displacement of the iron atom in this system prevents the dz2 orbital from overlapping effectively with the corrole a′ HOMO, leading to metal-corrole ferromagnetic coupling: Nardis, S.; Paolesse, R.; Licoccia, S.; Fronczek, F. R.; Vicente, M. G. H.; Shokhireva, T. K.; Cai, S.; Walker, F. A. Inorg. Chem. 2005, 44, 7030–7046. (11) (a) Groves, J. T. In Cytochrome P450: Structure, Mechanism, and Biochemistry, 3rd ed.; Ortiz de Montellano, P. R., Ed.; Kluwer/Plenum: New York, 2005; pp 1-43. (b) Shaik, S.; de Visser, S. P. In Cytochrome P450: Structure, Mechanism, and Biochemistry, 3rd ed.; Ortiz de Montellano, P. R., Ed.; Kluwer/Plenum: New York, 2005; pp 45-85. |
| URI: | http://wrap.warwick.ac.uk/id/eprint/29073 |
Data sourced from Thomson Reuters' Web of Knowledge
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