Special Issue "Metallocene Complexes"

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (31 July 2018)

Special Issue Editor

Guest Editor
Prof. Karlheinz Sünkel

Department of Chemistry, Ludwig-Maximilians-University Munich, Butenandtstr. 9, 81377 München, Germany
Website | E-Mail
Interests: organometallic chemistry; metallocene chemistry; coordination chemistry of polyfunctional ligands; cyclopentadienyl complexes

Special Issue Information

Dear Colleagues,

The discovery and characterization of ferrocene, (η5-C5H5)2Fe, marked the beginning of a new era of organometallic chemistry, and the event of its 65th birthday is celebrated by a Special Issue of the European Journal of Inorganic Chemistry in January, 2017. It was impressively shown that the introduction of all kinds of functional ring substituents into cyclopentadienyl ligands afford a tremendous variability in applications of this unique molecule. However, already, back in the 1950s, it was discovered that variations in the structural motif “(η5-C5H5)2Fe” were, not only possible by the introduction of ring substituents, but also by exchanging the iron with other metals: The large family of the (true) “metallocenes”, i.e., compounds of the type “Cp2M” had come to life. Meanwhile, such compounds are known for most (main-group and transition) metals, and, although most of them are less stable than ferrocene and also have different structures, they have still found numerous applications. This Special Issue aims to show that fascinating metallocene chemistry is not restricted to ferrocene alone.

Prof. Karlheinz Sünkel
Guest Editor

Manuscript Submission Information

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Keywords

  • metallocenes
  • metallocenium chemistry
  • macromolecular chemistry
  • bio-inorganic chemistry
  • catalysis

Published Papers (4 papers)

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Research

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Open AccessArticle Metalation Studies on Titanocene Dithiolates
Received: 18 July 2018 / Revised: 20 August 2018 / Accepted: 22 August 2018 / Published: 24 August 2018
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Abstract
Titanocene bis-arylthiolates [(C5H4X)(C5H4Y)Ti(SC6H4R)2] (X,Y = H, Cl; R = H, Me) can be prepared from the corresponding titanocene dichlorides by reacting with the thiols in the presence of DABCO
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Titanocene bis-arylthiolates [(C5H4X)(C5H4Y)Ti(SC6H4R)2] (X,Y = H, Cl; R = H, Me) can be prepared from the corresponding titanocene dichlorides by reacting with the thiols in the presence of DABCO as a base. They react with n-butyl lithium to give unstable Ti(III) radical anions. While the unsubstituted thiolates (X = Y = R = H) react with lithium Di-isopropylamide by decomposing to dimeric fulvalene-bridged and thiolate-bridged Ti(III) compounds, the ring-chlorinated compounds can be deprotonated with LDA and give appropriate electrophiles di-substituted and tri-substituted titanocene dithiolates. Full article
(This article belongs to the Special Issue Metallocene Complexes)
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Open AccessArticle Synthesis of Ferrocenyl-Substituted Organochalcogenyldichlorogermanes
Received: 13 June 2018 / Revised: 6 July 2018 / Accepted: 9 July 2018 / Published: 11 July 2018
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Abstract
Reaction of the isolable ferrocenyldichlorogermyl anion, Fc*GeCl2 (Fc* = 2,5-bis(3,5-di-t-butylphenyl)-1-ferrocenyl), with the isolable chalcogenenyl halides resulted in the formation of the corresponding organochalcogenyldichlorogermanes that were structurally characterized. Thus, it was demonstrated the use of sterically demanding ferrocenyl groups allowed
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Reaction of the isolable ferrocenyldichlorogermyl anion, Fc*GeCl2 (Fc* = 2,5-bis(3,5-di-t-butylphenyl)-1-ferrocenyl), with the isolable chalcogenenyl halides resulted in the formation of the corresponding organochalcogenyldichlorogermanes that were structurally characterized. Thus, it was demonstrated the use of sterically demanding ferrocenyl groups allowed isolating stable crystalline organochalcogenyldichlorogermanes. Full article
(This article belongs to the Special Issue Metallocene Complexes)
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Open AccessArticle Unexpected Formation and Structural Characterization of a Dinuclear Sodium Half-Sandwich Complex
Received: 12 April 2018 / Revised: 4 May 2018 / Accepted: 7 May 2018 / Published: 9 May 2018
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Abstract
Treatment of N,N′-diisopropylcarbodiimide with sodium cyclopentadienide (NaCp) in a molar ratio of 1:1 in THF solution resulted in formation of the unexpected dinuclear sodium half-sandwich complex [NaC5H3{C(NHiPr)(=NiPr)}2-1,2]2 (1
[...] Read more.
Treatment of N,N′-diisopropylcarbodiimide with sodium cyclopentadienide (NaCp) in a molar ratio of 1:1 in THF solution resulted in formation of the unexpected dinuclear sodium half-sandwich complex [NaC5H3{C(NHiPr)(=NiPr)}2-1,2]2 (1) as colorless crystals in low yield. The newly formed ligand, which belongs to the group of 6-aminofulvene-2-aldiminate ligands, coordinates to sodium in an η5-coordination mode via the cyclopentadienyl ring. Dimerization occurs through additional chelating κN,N′-coordination of the amidine substituents. The NMR data of 1 indicated a slow dimer/monomer equilibrium in solution. A serendipitously isolated hydrolysis product, {µ-(iPrNH)2C=O}2[NaC5H3{C(NHiPr)(=NiPr)}2-1,2]2 (2), contains the new 6-aminofulvene-2-aldiminate ligand in the N,N′-chelating coordination mode with the cyclopentadiene ring being uncoordinated. In this case, dimerization occurs through the presence of two bridging neutral N,N′-diisopropylurea ligands. Both compounds have been structurally characterized by single-crystal X-ray diffraction. Full article
(This article belongs to the Special Issue Metallocene Complexes)
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Review

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Open AccessReview Group 4 Metallocene Polymers—Selected Properties and Applications
Received: 27 May 2018 / Revised: 16 June 2018 / Accepted: 20 June 2018 / Published: 26 June 2018
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Abstract
Group 4 metallocene polymers offer a wide variety of unique properties. Some of these are reviewed in this paper, including the ability to form fibers and to absorb laser radiation, thereby protecting materials containing them in small amounts; the possibility of becoming conductive
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Group 4 metallocene polymers offer a wide variety of unique properties. Some of these are reviewed in this paper, including the ability to form fibers and to absorb laser radiation, thereby protecting materials containing them in small amounts; the possibility of becoming conductive materials through simple doping; increasing the productivity of damaged, old and mold-infested seeds through incorporation of plant growth hormones; and acting as anticancer drugs that inhibit a variety of human cancers including breast and pancreatic cancers. Full article
(This article belongs to the Special Issue Metallocene Complexes)
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