Magnetic Anisotropy of Dichlorobis(η5‐cyclopentadienyl) Complexes of Vanadium,Niobium, and Tantalum |
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Authors: | Maurits Kuiper Manfred Speldrich Helmut Schilder Prof. Dr. Heiko Lueken |
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Affiliation: | Institute of Inorganic Chemistry, RWTH Aachen University, 52074 Aachen, Germany |
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Abstract: | Abstract. The magnetic behavior of the mononuclear nd1 systems MCp2Cl2 (M = V4+[3d1], Nb4+[4d1], Ta4+[5d1], space group P21/c, pseudosymmetry of the molecules C2v) deviates from pure single ion spin magnetism on account of ligand field effect (Hlf), spin‐orbit coupling (Hso), and intermolecular spin‐spin exchange interactions (Hex). For both VCp2Cl2 and NbCp2Cl2 excellent adaptations to the measured susceptibility data were obtained (2 K ≤ T ≤ 300 K) on the basis of spectroscopic data (lf, so) and cooperative metal–metal interactions (ex) of antiferromagnetic nature [molecular field model (mf)]. For TaCp2Cl2 experimental term structure data are not available. Therefore, Jørgensen's spectroscopical series (g‐factor of the central ion) was applied to extrapolate the data set for TaCp2Cl2. Hlf, Hso, and Hex (antiferromagnetic) increase in the order 3d1 → 4d1 → 5d1 leading, with rising atomic number of the metals, to a distinct enhancement of the magnetic anisotropy. At 4 K the μeff components μeff,y (oriented perpendicular to the cg–M–cg plane; “cg” = center of gravity of the Cp ring), μeff,z (oriented along the twofold pseudoaxis), and μeff,x are 1.73, 1.69, 1.68 (V), 1.73, 1.62, 1.59 (Nb), and 1.71, 1.59, 1.49 (Ta). While μeff,y is independent of T, both μeff,z and μeff,x decrease with decreasing T. |
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Keywords: | Transition metals Metallocene dichlorides Vanadium Niobium Tantalum Magnetic anisotropy |
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