Design and synthesis of a dinucleating ligand system with varying terminal donor functions that provides no bridging donor and its application to the synthesis of a series of Fe-III-mu-O-Fe-III complexes

Strautmann J, Dammers S, Limpke T, Parthier J, Zimmermann T, Walleck S, Heinze-Brückner G, Stammler A, Bögge H, Glaser T (2016)
DALTON TRANSACTIONS 45(8): 3340-3361.

Journal Article | Published | English

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Abstract
Based on a rational ligand design for stabilizing high-valent {Fe(mu-O)(2)Fe} cores, a new family of dinucleating bis(tetradentate) ligands with varying terminal donor functions has been developed: redox-inert biomimetic carboxylates in H(4)julia, pyridines in susan, and phenolates in H(4)hilde(Me2). Based on a retrosynthetic analysis, the ligands were synthesized and used for the preparation of their diferric complexes [(julia){Fe(OH2)(mu-O)Fe(OH2)}]center dot 6H(2)O, [(julia){Fe(OH2)(mu-O)Fe(OH2)}]center dot 7H(2)O, [(julia){Fe(DMSO)(mu-O)Fe(DMSO)}]center dot 3DMSO, [(hilde(Me2)){Fe(mu-O)Fe}]center dot CH2Cl2, [(hilde(Me2)){FeCl}(2)]center dot 2CH(2)Cl(2), [(susan){FeCl(mu-O)FeCl}]Cl-2 center dot 2H(2)O, [(susan){FeCl(mu-O)FeCl0.75(OCH3)(0.25)}](ClO4)(2)center dot 0.5MeOH, and [(susan){FeCl(mu-O)FeCl}](ClO4)(2)center dot 0.5EtOH, which were characterized by single-crystal X-ray diffraction, FTIR, UV-Vis-NIR, Massbauer, magnetic, and electrochemical measurements. The strongly electron-donating phenolates afford five-coordination, while the carboxylates and pyridines lead to six-coordination. The analysis of the ligand conformations demonstrates a strong flexibility of the ligand backbone in the complexes. The different hydrogen-bonding in the secondary coordination sphere of [(julia){Fe(OH2)(mu-O)Fe(OH2)}] influences the C-O, C=O, and Fe-O bond lengths and is reflected in the FTIR spectra. The physical properties of the central {Fe(mu-O)Fe} core (d-d, mu-oxo -> Fe-III CT, nu(as)(Fe-O-Fe), J) are governed by the differences in terminal ligands - Fe-III bonds: strongly covalent pi-donation with phenolates, less covalent pi-donation with carboxylates, and pi-acceptation with pyridines. Thus, [(susan){FeCl(mu-O)FeCl}](2+) is oxidized at 1.48 V vs. Fc(+)/Fc, which is shifted to 1.14 V vs. Fc(+)/Fc by methanolate substitution, while [(julia){Fe(OH2)(mu-O) Fe(OH2)}] is oxidized <= 1 V vs. Fc(+)/Fc. [(hilde(Me2)){Fe(mu-O)Fe}] is oxidized at 0.36 V vs. Fc(+)/Fc to a phenoxyl radical. The catalytic oxidation of cyclohexane with TONs up to 39.5 and 27.0 for [(susan){FeCl(mu-O)FeCl}](2+) and [(hilde(Me2)){Fe(mu-O)Fe}], respectively, indicates the potential to form oxidizing intermediates.
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Strautmann J, Dammers S, Limpke T, et al. Design and synthesis of a dinucleating ligand system with varying terminal donor functions that provides no bridging donor and its application to the synthesis of a series of Fe-III-mu-O-Fe-III complexes. DALTON TRANSACTIONS. 2016;45(8):3340-3361.
Strautmann, J., Dammers, S., Limpke, T., Parthier, J., Zimmermann, T., Walleck, S., Heinze-Brückner, G., et al. (2016). Design and synthesis of a dinucleating ligand system with varying terminal donor functions that provides no bridging donor and its application to the synthesis of a series of Fe-III-mu-O-Fe-III complexes. DALTON TRANSACTIONS, 45(8), 3340-3361.
Strautmann, J., Dammers, S., Limpke, T., Parthier, J., Zimmermann, T., Walleck, S., Heinze-Brückner, G., Stammler, A., Bögge, H., and Glaser, T. (2016). Design and synthesis of a dinucleating ligand system with varying terminal donor functions that provides no bridging donor and its application to the synthesis of a series of Fe-III-mu-O-Fe-III complexes. DALTON TRANSACTIONS 45, 3340-3361.
Strautmann, J., et al., 2016. Design and synthesis of a dinucleating ligand system with varying terminal donor functions that provides no bridging donor and its application to the synthesis of a series of Fe-III-mu-O-Fe-III complexes. DALTON TRANSACTIONS, 45(8), p 3340-3361.
J. Strautmann, et al., “Design and synthesis of a dinucleating ligand system with varying terminal donor functions that provides no bridging donor and its application to the synthesis of a series of Fe-III-mu-O-Fe-III complexes”, DALTON TRANSACTIONS, vol. 45, 2016, pp. 3340-3361.
Strautmann, J., Dammers, S., Limpke, T., Parthier, J., Zimmermann, T., Walleck, S., Heinze-Brückner, G., Stammler, A., Bögge, H., Glaser, T.: Design and synthesis of a dinucleating ligand system with varying terminal donor functions that provides no bridging donor and its application to the synthesis of a series of Fe-III-mu-O-Fe-III complexes. DALTON TRANSACTIONS. 45, 3340-3361 (2016).
Strautmann, Julia, Dammers, Susanne, Limpke, Thomas, Parthier, Janine, Zimmermann, Thomas, Walleck, Stephan, Heinze-Brückner, Gabriele, Stammler, Anja, Bögge, Hartmut, and Glaser, Thorsten. “Design and synthesis of a dinucleating ligand system with varying terminal donor functions that provides no bridging donor and its application to the synthesis of a series of Fe-III-mu-O-Fe-III complexes”. DALTON TRANSACTIONS 45.8 (2016): 3340-3361.
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