Article (Scientific journals)
A density functional theory calculation of the electronic properties of several high-spin and low-spin iron(II) pyrazolylborate complexes
Remacle, Françoise; Long, G. J.; Grandjean, Fernande
2008In Inorganic Chemistry, 47 (10), p. 4005-4014
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Abstract :
[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
Volume :
47
Issue :
10
Pages :
4005-4014
Peer reviewed :
Peer Reviewed verified by ORBi
Available on ORBi :
since 05 January 2010

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