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• W2034204615 startingPage "8013" @default.
• W2034204615 abstract "Abstract The cyano‐substituted metallocenes [M(C 5 H 4 CN) 2 ] (M=Fe, 1 ; Co, 2 ; Ni 3 ) and [M(C 5 Me 5 )(C 5 H 4 CN)] (M=Fe, 4 ; Co, 5 ; Ni, 6 ) were synthesized in yields up to 58 % by treating K(C 5 H 4 CN) or Tl(C 5 H 4 CN) with suitable transition‐metal precursors. Cyclic voltammetry indicated that the oxidation and reduction potentials of all the cyanometallocenes were shifted to positive values by up to 0.8 V. Single‐crystal X‐ray structure analysis showed that 1 had eclipsed ligands, formed planes in the lattice, and—unlike usual metallocenes—lined up in stacks perpendicular to these planes. Powder X‐ray studies established that 1 and 2 are isotypic. The 1 H and 13 C NMR spectra were recorded for all the new compounds. Signal shifts of up to δ =1500 ppm were recorded for the paramagnetic molecules 2 and 3 and were, at a given temperature, strikingly different for solution and solid‐state spectra. These results pointed to antiferromagnetic interactions as a consequence of molecular ordering in the lattice, as confirmed by magnetic measurements. The temperature‐dependent susceptibilities were reproduced by Heisenberg spin‐chain models ( H =− J $mathrel{mathop{sum}limits^{n- 1}limits_{i=1}}$ S i S i +1 ), thus yielding J =−28.3 and −10.3 cm −1 for 2 and 3 , respectively, whereas J=− 11.8 cm −1 was obtained for 3 from the Ising spin‐chain model. In accordance with molecular orbital (MO) considerations, much spin density was found to be delocalized not only on the cyclopentadienyl ligand but also the cyano substituents. The magnetic interaction was interpreted as a Heitler–London spin exchange and was analyzed based on how the interaction depends on the singly occupied MOs and the shift of parallel metallocenes relative to each other." @default.
• W2034204615 created "2016-06-24" @default.
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• W2034204615 date "2008-09-01" @default.
• W2034204615 modified "2023-10-17" @default.
• W2034204615 title "Crystal-Packing-Induced Antiferromagnetic Interactions of Metallocenes: Cyanonickelocenes, -cobaltocenes, and -ferrocenes" @default.
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• W2034204615 doi "https://doi.org/10.1002/chem.200701538" @default.
• W2034204615 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/18645991" @default.
• W2034204615 hasPublicationYear "2008" @default.
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