Synthesis, characterization, and reactivity of furan- and thiophene-functionalized bis(n-heterocyclic carbene) complexes of iron(II)
Type
ArticleAuthors
Rieb, JuliaRaba, Andreas
Haslinger, Stefan
Kaspar, Manuel
Pöthig, Alexander
Cokoja, Mirza
Basset, Jean-Marie

Kühn, Fritz
KAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2014-09-04Online Publication Date
2014-09-04Print Publication Date
2014-09-15Permanent link to this record
http://hdl.handle.net/10754/563759
Metadata
Show full item recordAbstract
The synthesis of iron(II) complexes bearing new heteroatom-functionalized methylene-bridged bis(N-heterocyclic carbene) ligands is reported. All complexes are characterized by single-crystal X-ray diffraction (SC-XRD), nuclear magnetic resonance (NMR) spectroscopy, and elemental analysis. Tetrakis(acetonitrile)-cis-[bis(o-imidazol-2-ylidenefuran)methane]iron(II) hexafluorophosphate (2a) and tetrakis(acetonitrile)-cis-[bis(o-imidazol-2-ylidenethiophene)methane]iron(II) hexafluorophosphate (2b) were obtained by aminolysis of [Fe{N(SiMe3)2}2(THF)] with furan- and thiophene-functionalized bis(imidazolium) salts 1a and 1b in acetonitrile. The SC-XRD structures of 2a and 2b show coordination of the bis(carbene) ligand in a bidentate fashion instead of a possible tetradentate coordination. The four other coordination sites of these distorted octahedral complexes are occupied by acetonitrile ligands. Crystallization of 2a in an acetone solution by the slow diffusion of Et2O led to the formation of cisdiacetonitriledi[ bis(o-imidazol-2-ylidenefuran)methane]iron(II) hexafluorophosphate (3a) with two bis(carbene) ligands coordinated in a bidentate manner and two cis-positioned acetonitrile molecules. Compounds 2a and 2b are the first reported iron(II) carbene complexes with four coordination sites occupied by solvent molecules, and it was demonstrated that those solvent ligands can undergo ligand-exchange reactions.Citation
Rieb, J., Raba, A., Haslinger, S., Kaspar, M., Pöthig, A., Cokoja, M., … Kühn, F. E. (2014). Synthesis, Characterization, and Reactivity of Furan- and Thiophene-Functionalized Bis(N-heterocyclic carbene) Complexes of Iron(II). Inorganic Chemistry, 53(18), 9598–9606. doi:10.1021/ic500959mSponsors
The authors gratefully acknowledge support and funding from the KAUST, the EU project Next-GTL, and the Technische Universitat Munchen Graduate School. J.R. thanks the Studienstiftung des deutschen Volkes for financial support.Publisher
American Chemical Society (ACS)Journal
Inorganic ChemistryRelations
Is Supplemented By:- [Dataset]
Rieb, J., Raba, A., Haslinger, S., Kaspar, M., Pöthig, A., Cokoja, M., … Kühn, F. E. (2015). CCDC 997387: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12gvs5. DOI: 10.5517/cc12gvs5 HANDLE: 10754/624312 - [Dataset]
Rieb, J., Raba, A., Haslinger, S., Kaspar, M., Pöthig, A., Cokoja, M., … Kühn, F. E. (2015). CCDC 997388: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12gvt6. DOI: 10.5517/cc12gvt6 HANDLE: 10754/624313 - [Dataset]
Rieb, J., Raba, A., Haslinger, S., Kaspar, M., Pöthig, A., Cokoja, M., … Kühn, F. E. (2015). CCDC 997389: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12gvv7. DOI: 10.5517/cc12gvv7 HANDLE: 10754/624314 - [Dataset]
Rieb, J., Raba, A., Haslinger, S., Kaspar, M., Pöthig, A., Cokoja, M., … Kühn, F. E. (2015). CCDC 997386: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12gvr4. DOI: 10.5517/cc12gvr4 HANDLE: 10754/624311
ae974a485f413a2113503eed53cd6c53
10.1021/ic500959m