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Heteroleptic, two-coordinate [M(NHC){N(SiMe 3 ) 2 }] (M = Co, Fe) complexes: synthesis, reactivity and magnetism rationalized by an unexpected metal oxidation state

DOI: 10.1039/C6DT03565E DOI Help

Authors: Andreas A. Danopoulos (Université de Strasbourg) , Pierre Braunstein (Université de Strasbourg) , Kirill Yu. Monakhov (RWTH Aachen University) , Jan Van Leusen (RWTH Aachen University) , Paul Kögerler (RWTH Aachen University; Jülich-Aachen Research Alliance (JARA-FIT) and Peter Grünberg Institute 6, Diamond Light Source) , Martin Clémancey (Equipe de Physicochimie des Métaux en Biologie) , Jean-marc Latour (Equipe de Physicochimie des Métaux en Biologie) , Anass Benayad (CEA/DRT/LITEN/DTNM/SEN/L2N) , Moniek Tromp (University of Amsterdam) , Elixabete Rezabal (LCM, CNRS, Ecole Polytechnique, Université Paris-Saclay) , Gilles Frison (LCM, CNRS, Ecole Polytechnique, Université Paris-Saclay)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Dalton Trans. , VOL 46 , PAGES 1163 - 1171

State: Published (Approved)
Published: December 2016
Diamond Proposal Number(s): 8071

Open Access Open Access

Abstract: The linear, two-coordinate and isostructural heteroleptic [M(IPr){N(SiMe3)2}] (IPr = 1,3-bis(diisopropylphenyl)-imidazol-2-ylidene), formally MI complexes (M = Co, 3; Fe, 4) were obtained by the reduction of [M(IPr)Cl{N(SiMe3)2}] with KC8, or [Co(IPr){N(SiMe3)2}2] with mes*PH2, mes* = 2,4,6-tBu3C6H2. The magnetism of 3 and 4 implies CoII and FeII centres coupled to one ligand-delocalized electron, in line with XPS and XANES data; the ac susceptibility of 4 detected a pronounced frequency dependence due to slow magnetization relaxation. Reduction of [Fe(IPr)Cl{N(SiMe3)2}] with excess KC8 in toluene gave the heteronuclear ‘inverse-sandwich’ Fe–K complex 7, featuring η6-toluene sandwiched between one Fe0 and one K+ centre.

Subject Areas: Chemistry

Instruments: I20-Scanning-X-ray spectroscopy (XAS/XES)


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