A fifteen year contribution of computational studies carried out in close synergy with experiments is summarized. This interplay has allowed some important breakthroughs in the field of organolanthanide chemistry. The variety of different reaction mechanisms in lanthanide chemistry appear to be broader than the simple bond metathesis.
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Advances in lanthanide cyclononatetraenyl chemistry.
Chem Commun (Camb)
December 2024
Institute of Inorganic Chemistry (AOC), Karlsruhe Institute of Technology (KIT), Kaiserstr. 12, 76131, Karlsruhe, Germany.
Cyclononatetraenyl (Cnt) is a nine-membered monoanionic aromatic ligand. Despite its early discovery in 1963, it has been rarely utilised in coordination chemistry, which is mainly due to its large diameter and easy skeletal rearrangement. Only in 2017, the first lanthanide Cnt complex was synthesised, marking the beginning of a new era in organolanthanide chemistry.
View Article and Find Full Text PDFTetraphenylpentalenide organolanthanide complexes.
Chem Commun (Camb)
September 2024
Department of Chemistry, University of Bath, BA2 7AY, UK.
Article Synopsis
- The symmetrical 1,3,4,6-tetraphenylpentalenide serves as an effective ligand for stabilizing brightly colored bis(pentalenide) lanthanide sandwich complexes.
- These complexes are relatively easy to create and add to the existing knowledge of lanthanide organometallics.
- They also open up new avenues for investigating how f-orbitals influence electronic structure and bonding in these materials.
Organolanthanide Single-Molecule Magnets with Heterocyclic Ligands.
Angew Chem Int Ed Engl
September 2024
School of Chemistry, Frontier Institute of Science and Technology, State Key Laboratory of Electrical Insulation and Power Equipment, MOE Key Laboratory for Nonequilibrium Synthesis of Condensed Matter and Xi'an Key Laboratory of Electronic Devices and Material Chemistry, Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, 710054, P. R. China.
Lanthanide (Ln) based mononuclear single-molecule magnets (SMMs) provide probably the finest ligand regulation model for magnetic property. Recently, the development of such SMMs has witnessed a fast transition from coordination to organometallic complexes because the latter provides a fertile, yet not fully excavated soil for the development of SMMs. Especially those SMMs with heterocyclic ligands have shown the potential to reach higher blocking temperature.
View Article and Find Full Text PDFThe Tishchenko reaction mediated by organo-f-complexes: the myths and obstacles.
RSC Adv
May 2024
Advanced Catalysis Facility, Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology Vellore-632014 Tamil Nadu India
For over a century, the Tishchenko reaction has been a valuable technique for synthesizing esters from aldehydes, serving a variety of applications in different domains. Beyond the remarkable advances in organoactinide and organolanthanide chemistry over the past two decades, there has been a significant increase in the research of the electrophilic d0/fn chemistry of organoactinide and organolanthanide compounds due to the captivating interplay between their structure and reactivity, and their exceptional performance in various homogeneous catalytic processes. The remarkable influence of ligand design, both in terms of steric hindrance and electronic properties, on the catalytic activity of organo-f-element complexes in organic transformations is well-established.
View Article and Find Full Text PDFOn-Surface Synthesis of Organolanthanide Sandwich Complexes.
Adv Sci (Weinh)
June 2024
Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA Nanoscience), Madrid, 28049, Spain.
The synthesis of lanthanide-based organometallic sandwich compounds is very appealing regarding their potential for single-molecule magnetism. Here, it is exploited by on-surface synthesis to design unprecedented lanthanide-directed organometallic sandwich complexes on Au(111). The reported compounds consist of Dy or Er atoms sandwiched between partially deprotonated hexahydroxybenzene molecules, thus introducing a distinct family of homoleptic organometallic sandwiches based on six-membered ring ligands.
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