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Status: Bibliographieeintrag

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Verfasst von:Roquette, Pascal [VerfasserIn]   i
 Maronna, Astrid Christine [VerfasserIn]   i
 Peters, Anastasia [VerfasserIn]   i
 Kaifer, Elisabeth [VerfasserIn]   i
 Himmel, Hans-Jörg [VerfasserIn]   i
 Hauf, Christoph [VerfasserIn]   i
 Herz, Verena [VerfasserIn]   i
 Scheidt, Ernst-Wilhelm [VerfasserIn]   i
 Scherer, Wolfgang [VerfasserIn]   i
Titel:On the electronic structure of niII complexes that feature chelating bisguanidine ligands
Verf.angabe:Pascal Roquette, Astrid Maronna, Anastasia Peters, Elisabeth Kaifer, Hans-Jörg Himmel, Christoph Hauf, Verena Herz, Ernst-Wilhelm Scheidt, and Wolfgang Scherer
E-Jahr:2010
Jahr:20 January 2010
Umfang:15 S.
Fussnoten:Dedicated to Professor Hubert Schmidbaur on the occasion of his 75th birthday ; Gesehen am 16.06.2023
Titel Quelle:Enthalten in: Chemistry - a European journal
Ort Quelle:Weinheim : Wiley-VCH, 1995
Jahr Quelle:2010
Band/Heft Quelle:16(2010), 4, Seite 1336-1350
ISSN Quelle:1521-3765
Abstract:In this work we report on the syntheses and properties of several new Ni complexes featuring the chelating bisguanidines bis(tetramethylguanidino)benzene (btmgb), bis(tetramethylguanidino)naphthalene (btmgn), and bis(tetramethylguanidino)biphenyl (btmgbp) as ligands. All complexes were structurally characterized by single-crystal X-ray diffraction and quantum chemical calculations. A detailed inspection of the magnetic susceptibility of [(btmgb)NiX2] and [(btmgbp)NiX2] (X=Cl, Br) revealed a linear temperature dependence of χ−1(T) above 50 K, which was in agreement with a Curie-Weiss-type behavior and a triplet ground state. Below approximately 25 K, however, magnetic susceptibility studies of the paramagnetic d8 Ni complexes revealed the presence of a significant zero-field splitting (ZFS) that results from spin-orbit mixing of excited states into the triplet ground state. The electronic consequences that might arise from the mixing of states as well as from a possible non-innocent behavior of the ligand have been explored by an experimental charge density study of [(btmgb)NiCl2] at low temperatures (7 K). Here, the presence of ZFS was identified as one potential reason for the flat ∢Cl-Ni-Cl deformation potential and the distinct differences between the ∢X-Ni-X valence angles observed by experiment and predicted by DFT. An analysis of the topology of the experimentally and theoretically derived electron-density distributions of [(btmgb)NiCl2] confirmed the strong donor character of the bisguanidine ligand but clearly ruled out any significant non-innocent ligand (NIL) behavior. Hence, [(btmgb)NiCl2] provides an experimental reference system to study the mixing of certain excited states into the ground state unbiased from any competing NIL behavior.
DOI:doi:10.1002/chem.200901479
URL:Bitte beachten Sie: Dies ist ein Bibliographieeintrag. Ein Volltextzugriff für Mitglieder der Universität besteht hier nur, falls für die entsprechende Zeitschrift/den entsprechenden Sammelband ein Abonnement besteht oder es sich um einen OpenAccess-Titel handelt.

Volltext: https://doi.org/10.1002/chem.200901479
 Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.200901479
 DOI: https://doi.org/10.1002/chem.200901479
Datenträger:Online-Ressource
Sprache:eng
Sach-SW:chelates
 coordination compounds
 electron density
 guanidines
 nickel
K10plus-PPN:1850435235
Verknüpfungen:→ Zeitschrift

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