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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Abstract
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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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.
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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34 References

Data provided by Europe PubMed Central.

Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint
Reed, Chemical Reviews 88(6), 1988

Gagne, Inorganic Chemistry 19(9), 1980

Katz, Journal of the American Chemical Society 102(3), 1980

Blount, Journal of the American Chemical Society 95(21), 1973
Artificial molecular rotors.
Kottas GS, Clarke LI, Horinek D, Michl J., Chem. Rev. 105(4), 2005
PMID: 15826014
Electronic Coupling in Mixed-Valence Dinuclear Ferrocenes and Cobaltocenes with Saturated Bridging Groups
Jones, Chemistry - A European Journal 11(15), 2005
A synthetic route to borylene-bridged poly(ferrocenylene)s.
Heilmann JB, Scheibitz M, Qin Y, Sundararaman A, Jakle F, Kretz T, Bolte M, Lerner HW, Holthausen MC, Wagner M., Angew. Chem. Int. Ed. Engl. 45(6), 2006
PMID: 16385591
A Synthetic Route to Borylene-Bridged Poly(ferrocenylene)s
Heilmann, Angewandte Chemie 118(6), 2006
[m.m]Metallocenophane: Synthese, Struktur, Eigenschaften
Mueller-Westerhoff, Angewandte Chemie 98(8), 1986

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