Document Detail


Iron substitution for sodium in a carboxylate-bridged, heterodinuclear sodium-iron complex.
MedLine Citation:
PMID:  16287269     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
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.
Authors:
Jeremy J Kodanko; Dong Xu; Datong Song; Stephen J Lippard
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Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural    
Journal Detail:
Title:  Journal of the American Chemical Society     Volume:  127     ISSN:  0002-7863     ISO Abbreviation:  J. Am. Chem. Soc.     Publication Date:  2005 Nov 
Date Detail:
Created Date:  2005-11-18     Completed Date:  2006-02-14     Revised Date:  2013-06-24    
Medline Journal Info:
Nlm Unique ID:  7503056     Medline TA:  J Am Chem Soc     Country:  United States    
Other Details:
Languages:  eng     Pagination:  16004-5     Citation Subset:  IM    
Affiliation:
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
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MeSH Terms
Descriptor/Qualifier:
Carboxylic Acids / chemistry*
Iron / chemistry*
Molecular Structure
Sodium / chemistry*
Grant Support
ID/Acronym/Agency:
F32 GM069236-01/GM/NIGMS NIH HHS; GM32134/GM/NIGMS NIH HHS; R01 GM032134/GM/NIGMS NIH HHS; R01 GM032134-21/GM/NIGMS NIH HHS; R01 GM032134-24/GM/NIGMS NIH HHS
Chemical
Reg. No./Substance:
0/Carboxylic Acids; 7439-89-6/Iron; 7440-23-5/Sodium
Comments/Corrections

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