| Iron substitution for sodium in a carboxylate-bridged, heterodinuclear sodium-iron complex. | |
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MedLine Citation:
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PMID: 16287269 Owner: NLM Status: MEDLINE |
Abstract/OtherAbstract:
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The synthesis and structural characterization of the carboxylate-bridged, heterodinuclear iron-sodium complex [NaFe(PIC2DET)(mu-O2CTrp)3] (2), where PIC2DET (1) is a 2,3-diethynyltriptycene-linked dipicolinic methyl ester ligand and Trp is 9-triptycenyl, are described. The metal ions in 2 are bridged by three triptycene carboxylates with an Fe...Na distance of 3.181(2) A, and each is coordinated to a pyridine nitrogen and carbonyl oxygen atom of 1, forming two five-membered chelate rings. A linkage isomer in which Fe1 is bound by the other ester oxygen atom of 1 was identified by X-ray crystallographic analysis. Treatment of 2 with Fe(OTf)2.2MeCN resulted in substitution of sodium by iron(II) to give the cationic diiron(II) complex [Fe2(PIC2DET)(mu-O2CTrp)3][OTf] (3). This reaction was investigated by UV-vis, IR, MS, and stopped-flow spectroscopy. The substitution is first order with respect to 2 and zero order with respect to Fe(OTf)2.2MeCN (kobs = 21 +/- 2 s-1), consistent with a dissociative mechanism. A positive enthalpy of activation (DeltaH = 59 +/- 6 kJ mol-1) and negative entropy of activation (DeltaS = -20 +/- 6 J mol-1 K-1) were calculated from the temperature dependence of the rate-determining dissociation step. |
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Authors:
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Jeremy J Kodanko; Dong Xu; Datong Song; Stephen J Lippard |
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Publication Detail:
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Type: Journal Article; Research Support, N.I.H., Extramural |
Journal Detail:
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Title: Journal of the American Chemical Society Volume: 127 ISSN: 0002-7863 ISO Abbreviation: J. Am. Chem. Soc. Publication Date: 2005 Nov |
Date Detail:
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Created Date: 2005-11-18 Completed Date: 2006-02-14 Revised Date: 2013-04-12 |
Medline Journal Info:
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Nlm Unique ID: 7503056 Medline TA: J Am Chem Soc Country: United States |
Other Details:
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Languages: eng Pagination: 16004-5 Citation Subset: IM |
Affiliation:
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Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA. |
Export Citation:
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APA/MLA Format Download EndNote Download BibTex |
| MeSH Terms | |
Descriptor/Qualifier:
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Carboxylic Acids
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chemistry* Iron / chemistry* Molecular Structure Sodium / chemistry* |
| Grant Support | |
ID/Acronym/Agency:
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F32 GM069236-01/GM/NIGMS NIH HHS; GM32134/GM/NIGMS NIH HHS; R01 GM032134-21/GM/NIGMS NIH HHS; R01 GM032134-24/GM/NIGMS NIH HHS |
| Chemical | |
Reg. No./Substance:
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0/Carboxylic Acids; 7439-89-6/Iron; 7440-23-5/Sodium |
| Comments/Corrections | |
From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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