The trinuclear gallium-bridged ferrocenophane [{Fe(eta(5)-C5H4)(2)}(3)Ga-2]: Synthesis, bonding, structure, and coordination chemistry

Althoff A, Eisner D, Jutzi P, Lenze N, Neumann B, Schoeller W, Stammler H-G (2006)
CHEMISTRY-A EUROPEAN JOURNAL 12(21): 5471-5480.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
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Abstract / Bemerkung
The trinuclear ferrocenophane [{Fe(eta(5)-C5H4)(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)-C5H4)(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 3a-3d possessing linear donor-aceptor-aceptor-donor arrangements. Crystal structure data for 3a-3d show a symmetry-reduced chiral ferrocenophane core (D-3h -> D-3). A polymeric rodlike structure is observed for 3b and 3d caused by it-stacking effects (3b) or by a difunctional donor-acceptor interaction (3d). In solution, the chirality of the adducts is lost by rapid interconversion of the enantiomers. A cyclic voltammogram of 3b 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 3b are compared with those of other pyridine-stabilized gallyl-sustituted ferrocene derivatives and with ferrocene itself.
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CHEMISTRY-A EUROPEAN JOURNAL
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12
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21
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5471-5480
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Althoff A, Eisner D, Jutzi P, et al. The trinuclear gallium-bridged ferrocenophane [{Fe(eta(5)-C5H4)(2)}(3)Ga-2]: Synthesis, bonding, structure, and coordination chemistry. CHEMISTRY-A EUROPEAN JOURNAL. 2006;12(21):5471-5480.
Althoff, A., Eisner, D., Jutzi, P., Lenze, N., Neumann, B., Schoeller, W., & Stammler, H. - G. (2006). The trinuclear gallium-bridged ferrocenophane [{Fe(eta(5)-C5H4)(2)}(3)Ga-2]: Synthesis, bonding, structure, and coordination chemistry. CHEMISTRY-A EUROPEAN JOURNAL, 12(21), 5471-5480. doi:10.1002/chem.200600218
Althoff, A., Eisner, D., Jutzi, P., Lenze, N., Neumann, B., Schoeller, W., and Stammler, H. - G. (2006). The trinuclear gallium-bridged ferrocenophane [{Fe(eta(5)-C5H4)(2)}(3)Ga-2]: Synthesis, bonding, structure, and coordination chemistry. CHEMISTRY-A EUROPEAN JOURNAL 12, 5471-5480.
Althoff, A., et al., 2006. The trinuclear gallium-bridged ferrocenophane [{Fe(eta(5)-C5H4)(2)}(3)Ga-2]: Synthesis, bonding, structure, and coordination chemistry. CHEMISTRY-A EUROPEAN JOURNAL, 12(21), p 5471-5480.
A. Althoff, et al., “The trinuclear gallium-bridged ferrocenophane [{Fe(eta(5)-C5H4)(2)}(3)Ga-2]: Synthesis, bonding, structure, and coordination chemistry”, CHEMISTRY-A EUROPEAN JOURNAL, vol. 12, 2006, pp. 5471-5480.
Althoff, A., Eisner, D., Jutzi, P., Lenze, N., Neumann, B., Schoeller, W., Stammler, H.-G.: The trinuclear gallium-bridged ferrocenophane [{Fe(eta(5)-C5H4)(2)}(3)Ga-2]: Synthesis, bonding, structure, and coordination chemistry. CHEMISTRY-A EUROPEAN JOURNAL. 12, 5471-5480 (2006).
Althoff, Alexander, Eisner, Dirk, Jutzi, Peter, Lenze, Norman, Neumann, Beate, Schoeller, Wolfgang, and Stammler, Hans-Georg. “The trinuclear gallium-bridged ferrocenophane [{Fe(eta(5)-C5H4)(2)}(3)Ga-2]: Synthesis, bonding, structure, and coordination chemistry”. CHEMISTRY-A EUROPEAN JOURNAL 12.21 (2006): 5471-5480.

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