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rdf:type |
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lifeskim:mentions |
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pubmed:issue |
12
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pubmed:dateCreated |
2005-6-6
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pubmed:abstractText |
The synthesis of a low-spin six-coordinate iron(II) porphyrinate in which the two axial ligands are forced to have a relative perpendicular orientation has been successfully accomplished for the first time. The reaction of four-coordinate (tetramesitylporphinato)iron(II) with 2-methylimidazole leads to the preparation of [Fe(TMP)(2-MeHIm)(2)] which cocrystallizes with five-coordinate [Fe(TMP)(2-MeHIm)]. The six-coordinate complex accommodates the sterically crowded pair of imidazoles with a strongly ruffled core and relative perpendicular orientation. This leads to shortened equatorial bonds of 1.963(6) A and slightly elongated axial Fe-N bond lengths of 2.034(9) A that are about 0.04 A shorter and 0.03 A longer, respectively, in comparison to those of the bis-imidazole-ligated iron(II) species with parallel oriented axial ligands. The Mossbauer spectrum shows a pair of quadrupole doublets that can be assigned to the components of the cocrystallized crystalline solid. High-spin five-coordinate [Fe(TMP)(2-MeHIm)] has DeltaE(Q) = 2.25 mm/s and delta = 0.90 mm/s at 15 K. The quadrupole splitting, DeltaE(Q), for [Fe(TMP)(2-MeHIm)(2)] is 1.71 mm/s, and the isomer shift is 0.43 mm/s at 15 K. The quadrupole splitting value is significantly larger than that found for low-spin iron(II) derivatives with relative parallel orientations for the two axial ligands. Mossbauer spectra thus provide a probe for ligand orientation when structural data are otherwise not available.
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pubmed:grant |
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pubmed:commentsCorrections |
http://linkedlifedata.com/resource/pubmed/commentcorrection/15934765-11439043,
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pubmed:language |
eng
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pubmed:journal |
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pubmed:citationSubset |
IM
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pubmed:chemical |
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pubmed:status |
MEDLINE
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pubmed:month |
Jun
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pubmed:issn |
0020-1669
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pubmed:author |
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pubmed:issnType |
Print
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pubmed:day |
13
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pubmed:volume |
44
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
4346-58
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pubmed:dateRevised |
2010-12-3
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pubmed:meshHeading |
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pubmed:year |
2005
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pubmed:articleTitle |
Ligand orientation control in low-spin six-coordinate (porphinato)iron(II) species.
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pubmed:affiliation |
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
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pubmed:publicationType |
Journal Article,
Research Support, U.S. Gov't, P.H.S.,
Research Support, N.I.H., Extramural
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