Ferromagnetic behavior in linear charge-transfer complexes. Structural and magnetic characterization of octamethylferrocene salts: (Fe(C sub 5 Me sub 4 H) sub 2 ) sup sm bullet + (A) sup sm bullet minus (A = TCNE, TCNQ)

Journal Article · Wed Jul 26 04:00:00 EDT 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00314a012· OSTI ID:7003438

Miller, J S; Glatzhofer, D T; O'Hare, D M ^[1]; Reiff, W M ^[2]; Chakraborty, A; Epstein, A J ^[3]

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1. E.I. de Pont de Nemours and Co., Inc., Wilmington, DE (USA)
2. Northeastern Univ., Boston, MA (USA)
3. Ohio Sate Univ., Columbus (USA)

The reaction of Fe{sup II}({eta}{sup 5}-C{sub 5}Me{sub 4}H){sub 2} with cyano acceptors A (A = TCNE (tetracyanoethylene), TCNQ (7,7,8,8-tetracyano-p-quanodimethane), n-C{sub 4}(CN){sub 6} (n-hexacyanobutadiene), C{sub 6}(CN){sub 6} (tris(dicyanomethylene)cyclopropane), DDQ (2,3-dichloro-5,6-dicyanobenzoquinone), TCNQF{sub 4} (perfluoro-7,7,8,8-tetracyano-p-quinodimethane) results in formation of 1:1 charge-transfer salts of (Fe{sup III})(C{sub 5}Me{sub 4}H){sub 2}){sup {sm bullet}+}(A){sup {sm bullet}{minus}} composition. The TCNE and TCNQ complexes have been structurally characterized. The high-temperature magnetic susceptibility for polycrystalline samples of these complexes can be fit by the Curie-Qeiss law, {chi} = C(T-{theta}){sup {minus}1}, with {theta} = +0.5 {plus minus} 2.2 K, and {mu}{sub eff} ranges from 2.71 to 3.97 {mu}{sub B}, suggesting that the polycrystalline samples measured had varying degrees of orientation. The 7.0 K EPR spectrum of the radical cation exhibits an axially symmetric powder pattern with g{sub {parallel}} = 4.11 and g{sub {perpendicular}} = 1.42, and the EPR parameters are essentially identical with those reported for ferrocenium and decamethylferrocenium. No EPR spectrum is observed at 78 K. Akin to the (Fe(C{sub 5}Me{sub 5}){sub 2}){sup {sm bullet}+} salts, these salts have {sup 57}Fe Moessbauer spectra consistent with complete charge transfer; however, unlike the case for the former complexes, quadrupole splittings of 0.30 and 0.220 mm/s are observed at 4.8 and 298 K, respectively. The absence of strong interionic magnetic coupling for the (Fe(C{sub 5}Me{sub 4}H){sub 2}){sup {sm bullet}+} salts contrasts with the behavior of the (Fe(C{sub 5}Me{sub 5}){sub 2}){sup {sm bullet}+} salts. 26 refs., 13 figs., 8 tabs.

• OSTI ID: 7003438
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 28:15; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKANES
ALKENES
CHEMICAL PREPARATION
COMPLEXES
CRYSTAL STRUCTURE
CYANIDES
DATA
ETHYLENE
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
IRON COMPLEXES
METHANE
MOLECULAR STRUCTURE
NUMERICAL DATA
ORGANIC COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES