Source:http://linkedlifedata.com/resource/pubmed/id/17654625
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rdf:type | |
lifeskim:mentions | |
pubmed:issue |
2
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pubmed:dateCreated |
2007-12-25
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pubmed:abstractText |
The redox properties of MCl2 (M=Mn, Fe, Co) acetonitrile solvates were electrochemically and spectroscopically characterized. The three voltammogram waves at 0.86, 0.48, and 0.21 V versus SCE for FeCl(2) dissolved in MeCN are assigned as one-electron reduction potentials for [Fe(II)Cl(x)(NCMe)4-x]2-x (1<or=x<or=3), respectively, and only [Fe IICl3(NCMe)]- {and [Fe IICl4]2- (E o 1/2 =0.04 V vs. SCE), if present} has a potential sufficient for TCNE reduction. The presence in solution of [Fe II(NCMe)6]2+ was also spectroscopically confirmed. The reduction potentials of M IICl2 (M=Mn, Co) acetonitrile adducts were inadequate to reduce TCNE. FeCl2 reacts with TCNE in MeCN to form [Fe II{C4(CN)8}(NCMe)2] (4), which is composed of layers of octahedral Fe II ions equatorially bonded to the four terminal N atoms of the mu4-[C4(CN)8]2- ion, with trans-MeCN groups and with 15-membered rings. Formation of 4 requires the simultaneous presence of [TCNE]* and [Fe II(NCMe)6]2+ in solution, which is in contrast to when [(NEt4)2][Fe IICl4] was used to reduce TCNE. A reaction scheme is proposed. Paramagnetic [Fe II{C4(CN)8}(NCMe)2] exhibits substantial antiferromagnetic coupling (theta=-13.3 K), and orders as an antiferromagnet below 7.8 K. The irreversibility of zero-field and field-cooled magnetization suggests that the material exists below Tc in two magnetic states relatively close in energy, that is, the purely antiferromagnetic ground state and a slightly canted antiferromagnetic metastable state.
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pubmed:language |
eng
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pubmed:journal | |
pubmed:citationSubset |
IM
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pubmed:chemical |
http://linkedlifedata.com/resource/pubmed/chemical/Acetonitriles,
http://linkedlifedata.com/resource/pubmed/chemical/Butanes,
http://linkedlifedata.com/resource/pubmed/chemical/Ethylenes,
http://linkedlifedata.com/resource/pubmed/chemical/Ferrous Compounds,
http://linkedlifedata.com/resource/pubmed/chemical/Nitriles,
http://linkedlifedata.com/resource/pubmed/chemical/acetonitrile,
http://linkedlifedata.com/resource/pubmed/chemical/ferrous chloride,
http://linkedlifedata.com/resource/pubmed/chemical/tetracyanoethylene
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pubmed:status |
MEDLINE
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pubmed:issn |
0947-6539
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pubmed:author | |
pubmed:issnType |
Print
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pubmed:volume |
14
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
714-20
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pubmed:dateRevised |
2009-8-4
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pubmed:meshHeading |
pubmed-meshheading:17654625-Acetonitriles,
pubmed-meshheading:17654625-Butanes,
pubmed-meshheading:17654625-Crystallography, X-Ray,
pubmed-meshheading:17654625-Dimerization,
pubmed-meshheading:17654625-Electrochemistry,
pubmed-meshheading:17654625-Ethylenes,
pubmed-meshheading:17654625-Ferrous Compounds,
pubmed-meshheading:17654625-Models, Molecular,
pubmed-meshheading:17654625-Nitriles,
pubmed-meshheading:17654625-Oxidation-Reduction,
pubmed-meshheading:17654625-Spectrophotometry, Ultraviolet
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pubmed:year |
2008
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pubmed:articleTitle |
Acetonitrile-facilitated reductive dimerization of TCNE to octacyanobutanediide, [C4(CN)8]2-, by Iron(II) chloride.
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pubmed:affiliation |
Department of Chemistry, University of Utah, Salt Lake City, UT 84112-0850, USA.
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pubmed:publicationType |
Journal Article,
Research Support, Non-U.S. Gov't
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