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| Title: | A density functional calculation of the electric properties of several high-spin and low-spin iron(II) pyrazolylborate complexes |
| Author (s): | Remacle, Françoise Grandjean, Fernande Long, Gary John |
| Department/Lab Affiliations: | Chemistry |
| Keywords: | Density functional theory Mössbauer-effect electronic spin-state iron(II) |
| Issue Date: | 2008 |
| Publisher: | American Chemical Society ACS |
| Citation: | F. Remacle, F. Grandjean, and G. J. Long. A Density Functional Calculation of the Electric Properties of Several High-Spin and Low-Spin Iron(II) Pyrazolylborate Complexes, Inorganic Chemistry., Vol. 47(10), 2008. |
| Abstract: | Density functional theory has been used to study the electronic spin-state properties of low-spin Fe[HB(pz)3]2, high-spin Fe[HB(3-Mepz)3]2, high-spin Fe[HB(3,5-Me2pz)3]2, and high-spin Fe[HB(3,4,5-Me3pz)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 Mössbauer-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-methyl−H···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. |
| Type: | Article - Journal text |
| In Title: | Inorganic Chemistry |
| Copyright Notice: | Pre-print: author cannot archive; Post-print: author cannot archive; This material is presented to ensure timely dissemination of scholarly and technical work. Copyright and all rights therein are retained by authors or by other copyright holders. All persons copying this information are expected to adhere to the terms and constraints invoked by each author's copyright. In most cases, these works may not be reposted without the explicit permission of the copyright holder. FULL COPYRIGHT INFORMATION: |
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| title | A density functional calculation of the electric properties of several high-spin and low-spin iron(II) pyrazolylborate complexes |
| contributor.author | Remacle, Françoise |
| contributor.author | Grandjean, Fernande |
| contributor.author | Long, Gary John |
| contributor.deptlab | Chemistry |
| contributor.sponsor | Fonds de la Recherche Fondamentale Collective |
| contributor.sponsor | Ministère de la Région Wallonne |
| subject | Density functional theory |
| subject | Mössbauer-effect |
| subject | electronic spin-state |
| subject | iron(II) |
| date.issued | 2008 |
| publisher | American Chemical Society ACS |
| identifier.citation | F. Remacle, F. Grandjean, and G. J. Long. A Density Functional Calculation of the Electric Properties of Several High-Spin and Low-Spin Iron(II) Pyrazolylborate Complexes, Inorganic Chemistry., Vol. 47(10), 2008. |
| identifier.pub.URI | |
| description.abstract | Density functional theory has been used to study the electronic spin-state properties of low-spin Fe[HB(pz)3]2, high-spin Fe[HB(3-Mepz)3]2, high-spin Fe[HB(3,5-Me2pz)3]2, and high-spin Fe[HB(3,4,5-Me3pz)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 Mössbauer-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-methyl−H···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. |
| type | Article - Journal |
| type.DCMIType | text |
| type.status | Postprint |
| rights | Pre-print: author cannot archive; Post-print: author cannot archive; |
| rights | This material is presented to ensure timely dissemination of scholarly and technical work. Copyright and all rights therein are retained by authors or by other copyright holders. All persons copying this information are expected to adhere to the terms and constraints invoked by each author's copyright. In most cases, these works may not be reposted without the explicit permission of the copyright holder. |
| rights.URI | |
| rights.URI | |
| relation.isPartOf | Inorganic Chemistry |
| date.available | 2008-06-20T19:01:06Z |
| identifier.persist.URI |