Preparation and properties of stacked oligomeric and polymeric metallocenes

Arnold, Regina.; Matchett, Stephen A.; Rosenblum, M.

doi:10.1021/om00101a002

Cited by 56 publications

(29 citation statements)

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“…Whereas the synthesis of 5 was performed as reported by Rosenblum and co-workers, [15] the decamethylated iron…”

Section: Resultsmentioning

confidence: 99%

“…The twist of the naphthalene bridges, common to 1,8-bismetallocenylsubstituted naphthalenes, is caused by the repulsion of the two naphthalene-bonded Cp ligands. [11,13,14,15,17,19] The magnitude of the twist correlates roughly with the relative electron density on the naphthalene bonded Cp rings, which is demonstrated by the angle between the best planes of the Cp ligands. It is smallest for the dicationic species 1 and 3, 20.3 and 22.18, respectively, and increases for the neutral compounds 2 and 5.…”

Section: Molecular Structuresmentioning

confidence: 85%

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Electronic Coupling through Intramolecular π–π Interactions in Biscobaltocenes: A Structural, Spectroscopic, and Magnetic Study

Pagels¹,

Albrecht²,

Görlitz³

et al. 2011

Chemistry A European J

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The paramagnetic dinuclear complexes 1,8-bis(cobaltocenyl)naphthalene (2) and 1,8-bis[(pentamethyl-η(5)-cyclopentadienyl)(η(5)-cyclopentadiendiyl)cobalt(II)]naphthalene (4) were synthesized. The molecular structures were characterized by X-ray structure analysis and consisted of two cobaltocenes linked through a distorted naphthalene clamp. Electronic interactions between the two cobalt atoms were observed by cyclic voltammetric studies. Superconducting quantum interference device (SQUID) measurements of the pure compounds and diluted in their diamagnetic iron derivatives, as well as variable-temperature NMR spectroscopy experiments in solution are presented. Magnetic measurements revealed an antiferromagnetic coupling of the electrons in complexes 2 and 4. From NMR spectroscopy experiments, Curie behavior in the temperature range from -60 to +60 °C can be deduced. The electronic structure and magnetic behavior is supported by results of broken-symmetry DFT and multireference calculations along with UV/Vis spectroscopic data, which revealed an intramolecular through space π-π interaction between the cobaltocene units.

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“…Whereas the synthesis of 5 was performed as reported by Rosenblum and co-workers, [15] the decamethylated iron…”

Section: Resultsmentioning

confidence: 99%

Section: Molecular Structuresmentioning

confidence: 85%

Electronic Coupling through Intramolecular π–π Interactions in Biscobaltocenes: A Structural, Spectroscopic, and Magnetic Study

Pagels¹,

Albrecht²,

Görlitz³

et al. 2011

Chemistry A European J

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“…π-Stacked metallocene polymers were obtained, as shown in Scheme 11. The treatment of 1,8-diiodonaphthalene 39 with 1,1'-ferrocenyldizinc chloride 40 by Negishi coupling afforded polymer P18 with a relatively low M n of 3600 (Arnold et al, 1988). The synthetic procedure was modified as follows: the treatment of bis(2-octyl)ferrocene 43 with NaN(SiMe 3 ) 2 and FeCl 2 provided the ferrocene-stacked polymer P19 with an M n of 18400 (Nugent & Rosenblum, 1993;Rosenblum et al, 1995;Hudson et al, 1999).…”

Section: Naphthalene-based Oligomers and Polymersmentioning

confidence: 99%

Synthesis of Aromatic-Ring-Layered Polymers

Morisaki¹,

Chujo²

2011

Optoelectronics - Materials and Techniques

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“…Most studies were performed for pure Fc system [424][425][426] 61ac, M_Fe). Later both Cp ligands of Fc complexes in Scheme 61 were substituted by its mono-alkyl derivative, C 5 H 4 -2-octyl, while Cp ligands in complexes with metal M (Fe or Ni) were not modified, so that a pure Fc system with all Cp ligands was replaced by a alternating sequence of complexes with two Cp or two Cp-octyl ligands [426,427] (61b, M = Fe or Ni).…”

Section: Fc and Hemi-ferrocene Complexes Inside A Polymer Chainmentioning

confidence: 99%

“…Another series of ruthenocene-containing systems, stacked oligomeric and polymeric metallocene on the basis of naphthalene, was also prepared [424] in analogy with their Fc analogs, see Scheme 61 and related discussion.…”

Section: Other Systems (Non-carbon Units Metal Complexes)mentioning

confidence: 99%