The trindene trianion

Katz, Thomas J.; SLUSAREK, W.

doi:10.1021/ja00523a025

Cited by 39 publications

(36 citation statements)

References 5 publications

(12 reference statements)

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“…[2] Traces of the trinuclear iron sandwich complex [Td 2 Fe 3 ], which is based on the triindene trianion (Td), have been detected by mass spectrometry. [4] Herein, we will describe the synthesis, characterization, and some chemistry of the trinuclear gallium-bridged ferrocenophane [{FeA C H T U N G T R E N N U N G (C 5 H 4 ) 2 } 3 Ga 2 ] in which three ferrocene-1,1'-diyl units are held together by gallium atoms.…”

Section: Introductionmentioning

confidence: 99%

The Trinuclear Gallium‐Bridged Ferrocenophane [{Fe(η⁵‐C₅H₄)₂}₃Ga₂]: Synthesis, Bonding, Structure, and Coordination Chemistry

Althoff

Eisner

Jutzi

et al. 2006

Chemistry A European J

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The trinuclear ferrocenophane [{Fe(eta(5)-C(5)H(4))(3)}(2)Ga(2)] (3) featuring two sp(2)-hybridized gallium atoms in bridging positions between three ferrocene-1,1'-diyl units represents a novel type of ferrocene derivative. Compound 3 is obtained by thermal treatment of 1,1'-bis(dimethylgallyl)ferrocene (1) in nondonor solvents or in diethyl ether as solvent and subsequent thermal decomplexation. The [1.1]ferrocenophane [{Fe(eta(5)-C(5)H(4))(2)}(2){GaMe}(2)] (2) is an intermediate in the formation of 3. The reaction of 3 with an excess of trimethylgallium leads back to 1 and proves the reversibility of the multistep reaction sequence. Theoretical calculations reveal a carousel-type D(3h) structure for 3. The compound can best be described as being composed of three only weakly interacting ferrocenediyl units covalently connected by gallium atoms without any pi-bond contribution in the Ga--C bonds. Owing to steric constraints 3 cannot be reduced to the dianion 3(2-), which would feature a Ga--Ga bond. Compound 3 represents a stereochemically rigid difunctional Lewis acid allowing the formation of the adducts 3 a-3 d possessing linear donor-aceptor-aceptor-donor arrangements. Crystal structure data for 3 a-3 d show a symmetry-reduced chiral ferrocenophane core (D(3h)-->D(3)). A polymeric rodlike structure is observed for 3 b and 3 d caused by pi-stacking effects (3 b) or by a difunctional donor-acceptor interaction (3 d). In solution, the chirality of the adducts is lost by rapid interconversion of the enantiomers. A cyclic voltammogram of 3 b in pyridine reveals three quasi-reversible oxidation steps at -356, -154, and 8 mV, indicating only weak electron delocalization in the cationic species. The redox potentials of the pyridine adduct 3 b are compared with those of other pyridine-stabilized gallyl-sustituted ferrocene derivatives and with ferrocene itself.

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Section: Introductionmentioning

confidence: 99%

The Trinuclear Gallium‐Bridged Ferrocenophane [{Fe(η⁵‐C₅H₄)₂}₃Ga₂]: Synthesis, Bonding, Structure, and Coordination Chemistry

Althoff

Eisner

Jutzi

et al. 2006

Chemistry A European J

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“…The only other reported cyclo(1,1′-oligoferrocene) is cyclo(1,1′-terferrocene) (cyclo [3]), recently observed as a side product during the synthesis of (ferrocene-1,1′-diyl)bis(Hphosphinic acids) 33,34 . To the best of our knowledge, the only other isolated cyclic ferrocene oligomers are isomeric cyclo(1,2-terferrocene)s 23,35 and cyclo(1,1′,2,2′-terferrocene) 36 . Given that traditional Ullmann conditions appear unsuitable for the formation of cyclic products, we noted with interest the rapid, solution-based Ullmann-like coupling of Zhang and co-authors 37 .…”

Section: Resultsmentioning

confidence: 99%

Oligomeric ferrocene rings

et al. 2016

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Cyclic oligomers comprising strongly interacting redox-active monomer units represent an unknown, yet highly desirable class of nanoscale materials. Here we describe the synthesis and properties of the first family of molecules belonging to this compound category-differently sized rings comprising only 1,1'-disubstituted ferrocene units (cyclo[n], n = 5-7, 9). Due to the close proximity and connectivity of centres (covalent Cp-Cp linkages; Cp = cyclopentadienyl) solution voltammograms exhibit well-resolved, separated 1e(-) waves. Theoretical interrogations into correlations based on ring size and charge state are facilitated using values of the equilibrium potentials of these transitions, as well as their relative spacing. As the interaction free energies between the redox centres scale linearly with overall ring charge and in conjunction with fast intramolecular electron transfer (∼10(7) s(-1)), these molecules can be considered as uniformly charged nanorings (diameter ∼1-2 nm).

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“…The trindene trianion (Td), the smallest C 3 ‐symmetric polycyclic conjugated hydrocarbon, was synthesized by Katz and Ślusarek in 1980 11. The use of Td as a metal bridging ligand is particularly favorable because strain is minimal as a consequence of the presence of only five‐ and six‐membered rings.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of the Prototypical Cyclic Metallocene Triad: Mixed‐Valence Properties of [(FeCp)₃(trindenyl)] Isomers

et al. 2008

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Die Mischung macht's: Die Verknüpfung dreier Ferrocen‐Einheiten zu einer starren cyclischen Anordnung ergibt die syn,syn,anti‐ und syn,syn,syn‐Isomere von [(FeCp)3(Trindenyl)] (siehe Bild), deren Kationen unterschiedliche Gemischtvalenzeigenschaften aufweisen: Beim syn,syn,anti‐Isomer finden sich mehrfache Intervalenz‐Transfer(IT)‐Absorptionen im Nah‐IR/IR‐Spektrum, beim syn,syn,syn‐Isomer tritt eine einzelne Bande im Vis/Nah‐IR‐Spektrum auf.

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The trindene trianion

Cited by 39 publications

References 5 publications

The Trinuclear Gallium‐Bridged Ferrocenophane [{Fe(η⁵‐C₅H₄)₂}₃Ga₂]: Synthesis, Bonding, Structure, and Coordination Chemistry

The Trinuclear Gallium‐Bridged Ferrocenophane [{Fe(η⁵‐C₅H₄)₂}₃Ga₂]: Synthesis, Bonding, Structure, and Coordination Chemistry

Oligomeric ferrocene rings

Synthesis of the Prototypical Cyclic Metallocene Triad: Mixed‐Valence Properties of [(FeCp)₃(trindenyl)] Isomers

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The trindene trianion

Cited by 39 publications

References 5 publications

The Trinuclear Gallium‐Bridged Ferrocenophane [{Fe(η5‐C5H4)2}3Ga2]: Synthesis, Bonding, Structure, and Coordination Chemistry

The Trinuclear Gallium‐Bridged Ferrocenophane [{Fe(η5‐C5H4)2}3Ga2]: Synthesis, Bonding, Structure, and Coordination Chemistry

Oligomeric ferrocene rings

Synthesis of the Prototypical Cyclic Metallocene Triad: Mixed‐Valence Properties of [(FeCp)3(trindenyl)] Isomers

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The Trinuclear Gallium‐Bridged Ferrocenophane [{Fe(η⁵‐C₅H₄)₂}₃Ga₂]: Synthesis, Bonding, Structure, and Coordination Chemistry

The Trinuclear Gallium‐Bridged Ferrocenophane [{Fe(η⁵‐C₅H₄)₂}₃Ga₂]: Synthesis, Bonding, Structure, and Coordination Chemistry

Synthesis of the Prototypical Cyclic Metallocene Triad: Mixed‐Valence Properties of [(FeCp)₃(trindenyl)] Isomers