Journal article
Formation of a Decanuclear Organometallic Dysprosium Complex via a Radical-Radical Cross-Coupling Reaction
Angewandte Chemie International Edition, Vol.63(46), e202411635
11/11/2024
DOI: 10.1002/anie.202411635
PMID: 38963679
Abstract
Over the years, polynuclear cyclic or torus complexes have attracted increasing interest due to their unique metal topologies and properties. However, the isolation of polynuclear cyclic organometallic complexes is extremely challenging due to their inherent reactivity, which stems from the labile and reactive metal-carbon bonds. In this study, the pyrazine ligand undergoes a radical-radical cross-coupling reaction leading to the formation of a decanuclear [(Cp*)20Dy10(L1)10]·12(C7H8) (1; where L1 = anion of 2-prop-2-enyl-2H-pyrazine) complex, where all DyIII metal centers are bridged by the anionic L1 ligand. Amongst the family of polynuclear Ln organometallic complexes bearing CpR2Lnx units, 1 features the highest nuclearity obtained to date. In-depth computational studies were conducted to elucidate the proposed reaction mechanism and formation of L1, while probing of the magnetic properties of 1, revealed slow magnetic relaxation upon application of a static dc field.Over the years, polynuclear cyclic or torus complexes have attracted increasing interest due to their unique metal topologies and properties. However, the isolation of polynuclear cyclic organometallic complexes is extremely challenging due to their inherent reactivity, which stems from the labile and reactive metal-carbon bonds. In this study, the pyrazine ligand undergoes a radical-radical cross-coupling reaction leading to the formation of a decanuclear [(Cp*)20Dy10(L1)10]·12(C7H8) (1; where L1 = anion of 2-prop-2-enyl-2H-pyrazine) complex, where all DyIII metal centers are bridged by the anionic L1 ligand. Amongst the family of polynuclear Ln organometallic complexes bearing CpR2Lnx units, 1 features the highest nuclearity obtained to date. In-depth computational studies were conducted to elucidate the proposed reaction mechanism and formation of L1, while probing of the magnetic properties of 1, revealed slow magnetic relaxation upon application of a static dc field.
Details
- Title: Subtitle
- Formation of a Decanuclear Organometallic Dysprosium Complex via a Radical-Radical Cross-Coupling Reaction
- Creators
- Muralee Murugesu - University of OttawaNeha Bajaj - University of OttawaAlexandros A Kitos - University of OttawaNiki Mavragani - University of OttawaNathan R Loutsch - University of South DakotaBess Vlaisavljevich - University of South Dakota
- Resource Type
- Journal article
- Publication Details
- Angewandte Chemie International Edition, Vol.63(46), e202411635
- DOI
- 10.1002/anie.202411635
- PMID
- 38963679
- NLM abbreviation
- Angew Chem Int Ed Engl
- ISSN
- 1521-3773
- eISSN
- 1521-3773
- Publisher
- WILEY-V C H VERLAG GMBH
- Grant note
- U.S. Department of Energy, Office of Science, Basic Energy Sciences: DE-SC0023022 NSF: OAC-1626516
N. B., A. A. K., N. M. and M. M. are grateful to the Canada Foundation for Innovation (CFI) and the Natural Sciences and Engineering Research Council of Canada (NSERC) for the financial support of this work. N. M. acknowledges the Stavros Niarchos Foundation for financial support through scholarships. B. V. and N. L. were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, in the Heavy-Element Chemistry program (Grant No. DE-SC0023022). Computations supporting this project were performed on the High-Performance Computing systems at the University of South Dakota, funded by NSF Award OAC-1626516. We also thank Dr. Daniel Chartrand and Dr. Thierry Marris for the collection of SCXRD data and the refinement of the crystallographic data.
- Language
- English
- Electronic publication date
- 07/04/2024
- Date published
- 11/11/2024
- Academic Unit
- Chemistry
- Record Identifier
- 9984652255202771
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