98%
921
2 minutes
20
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*)Dy(L1)] ⋅ 12(CH) (1; where L1 = anion of 2-prop-2-enyl-2H-pyrazine; Cp* = pentamethylcyclopentadienyl) complex, where all Dy metal centres are bridged by the anionic L1 ligand. Amongst the family of polynuclear Ln organometallic complexes bearing Cp Ln units (Cp = substituted cyclopentadienyl), 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.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1002/anie.202411635 | DOI Listing |
Angew Chem Int Ed Engl
November 2024
Department of Chemistry and Biomolecular Sciences, University of Ottawa, 10 Marie Curie, Ottawa, Ontario, K1N 6N5, Canada.
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*)Dy(L1)] ⋅ 12(CH) (1; where L1 = anion of 2-prop-2-enyl-2H-pyrazine; Cp* = pentamethylcyclopentadienyl) complex, where all Dy metal centres are bridged by the anionic L1 ligand.
View Article and Find Full Text PDFInorg Chem
August 2023
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People's Republic of China.
The organometallic compounds of lithium ions have garnered continuous interest as indispensable precursors for the syntheses of organometallic complexes of main-group metals, transition metals, lanthanide metals, and actinide metals. In this work, we present a strategy for the preparation of a series of polynuclear lithium complexes. This methodology features the utilization of organolithium reagents both as metal sources to coordinate with the ligands and as nucleophilic reagents to undergo nucleophilic addition to the C═N bonds of the ligands.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2023
Technical University of Munich, TUM School of Natural Sciences, Department of Chemistry, Chair of Inorganic and Metal-Organic Chemistry, Lichtenbergstraße 4, 85748, Garching, Germany.
The bimetallic, decanuclear Ni Ga -cluster of the formula [Ni (GaTMP) (μ -GaTMP) (μ -GaTMP)] (1, TMP=2,2,6,6-tetramethylpiperidinyl) reacts reversibly with dihydrogen under the formation of a series of (poly-)hydride clusters 2. Low-temperature 2D NMR experiments at -80 °C show that 2 consist of a mixture of a di- (2 ), tetra- (2 ) and hexahydride species (2 ). The structures of 2 and 2 are assessed by a combination of 2D NMR spectroscopy and DFT calculations.
View Article and Find Full Text PDFInorg Chem
February 2022
Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
Organic ligand-directed synthesis of metal-ion clusters with a well-defined number and arrangement of metal ions is an important subject toward the development of functional inorganic-organic nanohybrids. Here we report the synthesis of multinuclear Zn-oxo clusters using a triptycene-based rigid ligand (HL) featuring three metal-coordination sites arranged in a triangular shape. Upon complexation of HL with zinc acetate dihydrate, a decanuclear Zn-oxo cluster and multinuclear Zn-oxo clusters with a smaller number of Zn(II) ions were formed as the final product and its intermediates, respectively.
View Article and Find Full Text PDFChemistry
January 2022
Dipartimento di Scienze Fisiche e Chimiche, Università dell'Aquila, Via Vetoio, 2, Coppito, 67100, L'Aquila, Italy.
The structure of a decanuclear photo- and redox-active dendrimer based on Ru(II) polypyridine subunits, suitable as a light-harvesting multicomponent species for artificial photosynthesis, has been investigated by means of computer modelling. The compound has the general formula [Ru{(μ-dpp)Ru[(μ-dpp)Ru(bpy) ] } ](PF ) (Ru10; bpy=2,2'-bipyridine; dpp=2,3-bis(2'-pyridyl)pyrazine). The stability of possible isomers of each monomer was investigated by performing classical molecular dynamics (MD) and quantum mechanics (QM) simulations on each monomer and comparing the results.
View Article and Find Full Text PDF