Synthesis and characterization of divalent manganese, iron, and cobalt complexes in tripodal phenolate/N-heterocyclic carbene ligand environments

Beitrag in einer Fachzeitschrift
(Originalarbeit)


Details zur Publikation

Autorinnen und Autoren: Käß M, Hohenberger J, Adelhardt M, Zolnhofer E, Mossin S, Heinemann F, Sutter J, Meyer K
Zeitschrift: Inorganic Chemistry
Verlag: American Chemical Society
Jahr der Veröffentlichung: 2014
Band: 53
Heftnummer: 5
Seitenbereich: 2460-2470
ISSN: 0020-1669
eISSN: 1520-510X


Abstract

Two novel tripodal ligands, (BIMPN) and (MIMPN), combining two types of donor atoms, namely, NHC and phenolate donors, were synthesized to complete the series of N-anchored ligands, ranging from chelating species with tris(carbene) to tris(phenolate) chelating arms. The complete ligand series offers a convenient way of tuning the electronic and steric environment around the metal center, thus, allowing for control of the complex's reactivity. This series of divalent complexes of Mn, Fe, and Co was synthesized and characterized by H NMR, IR, and UV/vis spectroscopy as well as by single-crystal X-ray diffraction studies. Variable-temperature SQUID magnetization measurements in the range from 2 to 300 K confirmed high-spin ground states for all divalent complexes and revealed a trend of increasing zero-field splitting |D| from Mn(II), to Fe(II), to Co(II) complexes. Zero-field Fe Mössbauer spectroscopy of the Fe(II) complexes 3, 4, 8, and 11 shows isomer shifts δ that increase gradually as carbenes are substituted for phenolates in the series of ligands. From the single-crystal structure determinations of the complexes, the different steric demand of the ligands is evident. Particularly, the molecular structure of 1 - in which a pyridine molecule is situated next to the Mn-Cl bond - and those of azide complexes 2, 4, and 6 demonstrate the flexibility of these mixed-ligand derivatives, which, in contrast to the corresponding symmetrical TIMEN ligands, allow for side access of, e.g., organic substrates, to the reactive metal center. © 2013 American Chemical Society.


FAU-Autorinnen und Autoren / FAU-Herausgeberinnen und Herausgeber

Adelhardt, Mario
Lehrstuhl für Anorganische und Allgemeine Chemie
Heinemann, Frank Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie
Hohenberger, Johannes
Lehrstuhl für Anorganische und Allgemeine Chemie
Käß, Martina
Lehrstuhl für Anorganische und Allgemeine Chemie
Meyer, Karsten Prof. Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie
Sutter, Jörg Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie
Zolnhofer, Eva
Lehrstuhl für Anorganische und Allgemeine Chemie


Einrichtungen weiterer Autorinnen und Autoren

Technical University of Denmark / Danmarks Tekniske Universitet (DTU)


Zitierweisen

APA:
Käß, M., Hohenberger, J., Adelhardt, M., Zolnhofer, E., Mossin, S., Heinemann, F.,... Meyer, K. (2014). Synthesis and characterization of divalent manganese, iron, and cobalt complexes in tripodal phenolate/N-heterocyclic carbene ligand environments. Inorganic Chemistry, 53(5), 2460-2470. https://dx.doi.org/10.1021/ic4024053

MLA:
Käß, Martina, et al. "Synthesis and characterization of divalent manganese, iron, and cobalt complexes in tripodal phenolate/N-heterocyclic carbene ligand environments." Inorganic Chemistry 53.5 (2014): 2460-2470.

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Zuletzt aktualisiert 2019-19-08 um 13:04