The First 1,1‘-Digallylferrocene and a Rodlike, Polymeric Donor−Acceptor Complex:  Synthesis, Properties, and Structure of [Fe(η5-C5H4GaMe2)2]n and [Fe(η5-C5H4GaMe2)2(C12H8N2)]n,1

Althoff, Alexander; Jutzi, Peter; Lenze, Norman; Neumann, Beate; Stammler, and Anja; Stammler, Hans‐Georg

doi:10.1021/om020185d

Cited by 46 publications

(25 citation statements)

References 22 publications

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“…In the first variant 3 was prepared from a suspension of 1,1'-bis(dimethylgallyl)ferrocene (1) [5] in pxylene under elimination of trimethylgallium at 150 8C. In a second variant 3 was prepared by using the […”

Section: Resultsmentioning

confidence: 99%

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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: Resultsmentioning

confidence: 99%

“…The ferrocene derivatives [Fe(C 5 H 4 GaMe 2 ·Py) 2 ] (1·2 Py), [5] [FeA C H T U N G T R E N N U N G ({GaMe(Py)H 4 C 5 } 2 Fe)] (2 b), [3b] and [Fe({Ga(Py)H 4 C 5 } 3 Fe)] (3 b) are oxidized more easily than the parent ferrocene. The electron-donating ability decreases in the direction 1·2 Py > 3 b > 2 b.…”

Section: Electrochemistry Of 3 Bmentioning

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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“…For example, 13 [25] 1,1'-di(methylgallyl)ferrocene: d = 76.2 ppm [32] ). This upfield shift is characteristic of strained [n]metallocenophanes (for example, 4, C ipso : d = 44-45 ppm; [15] 1,2-bis(dimethylamino)-1,2-dibora[2]ferrocenophane, C ipso : d = 76.2 ppm [19] ).…”

Section: Summary and Outlook 5077mentioning

confidence: 99%

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

2007

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The structures, bonding, and ring-opening reactions of strained cyclic carbon-based molecules form a key component of standard textbooks. In contrast, the study of strained organometallic molecules containing transition metals is a much more recent development. A wealth of recent research has revealed fascinating nuances in terms of structure, bonding, and reactivity. Building on initial work on strained ferrocenophanes, a broad range of strained organometallic rings composed of a variety of different metals, pi-hydrocarbon ligands, and bridging elements has now been developed. Such strained species can potentially undergo ring-opening reactions to functionalize surfaces and ring-opening polymerization to form easily processed metallopolymers with properties determined by the presence of the metal and spacer. This Review summarizes the current state of knowledge on the preparation, structural characterization, electronic structure, and reactivity of strained organometallic rings with pi-hydrocarbon ligands and d-block metals.

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“…The molecular structure of 4a has Scheme 2. Three different routes to the dinuclear, threefold-aluminum-bridged ferrocenophane of type 4, of which 4a has been isolated previously by treatment of AlMe 2 Cl with 1,1Ј-dilithioferrocene. [6] already been described, and that of 4b was determined in the present work (vide infra).…”

Section: Resultsmentioning

confidence: 99%

“…In previous work, [1] we successfully introduced rational synthetic methods to prepare dipyridine adducts 1, 2 and 3 (Scheme 1), which, in contrast to their gallium congeners, [2][3][4][5] had not been known. Interestingly, other attempts in this field, in the absence of pyridine, have produced compounds such as 4 [6] and 5 [7] (Scheme 1), in which at least the central aluminum atoms possess rather unusual surroundings.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization and Reactivity of Dinuclear and Trinuclear Aluminum‐Bridged Ferrocenophanes

2009

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Ferrocene derivatives bearing substituents with aluminum in the 1,1′‐positions, in the absence of donor ligands, possess rather unusual structural features. Starting from various dipyridine adducts of such 1,1′‐disubstituted ferrocene derivatives, it proved possible to trap the pyridine as the adducts R3Al(py) and monitor the formation of dinuclear and trinuclear aluminum‐bridged ferrocenophanes in solution by NMR spectroscopy. For the first time, the dynamic behaviour of such complexes was studied and a complete set of NMR spectroscopic data has been reported. The dinuclear complex [Fe(η5‐C5H4)2]2Al3Et5 was characterized by X‐ray structural analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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The First 1,1‘-Digallylferrocene and a Rodlike, Polymeric Donor−Acceptor Complex: Synthesis, Properties, and Structure of [Fe(η⁵-C₅H₄GaMe₂)₂]_n and [Fe(η⁵-C₅H₄GaMe₂)₂(C₁₂H₈N₂)]_n^,¹

Cited by 46 publications

References 22 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

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

Synthesis, Characterization and Reactivity of Dinuclear and Trinuclear Aluminum‐Bridged Ferrocenophanes

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The First 1,1‘-Digallylferrocene and a Rodlike, Polymeric Donor−Acceptor Complex: Synthesis, Properties, and Structure of [Fe(η5-C5H4GaMe2)2]n and [Fe(η5-C5H4GaMe2)2(C12H8N2)]n,1

Cited by 46 publications

References 22 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

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

Synthesis, Characterization and Reactivity of Dinuclear and Trinuclear Aluminum‐Bridged Ferrocenophanes

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The First 1,1‘-Digallylferrocene and a Rodlike, Polymeric Donor−Acceptor Complex: Synthesis, Properties, and Structure of [Fe(η⁵-C₅H₄GaMe₂)₂]_n and [Fe(η⁵-C₅H₄GaMe₂)₂(C₁₂H₈N₂)]_n^,¹

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