Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2019

Farnaby, Joy H.; Chowdhury, Tajrian; Horsewill, Samuel J.; Wilson, Bradley; Jaroschik, Florian

doi:10.1016/j.ccr.2021.213830

Cited by 24 publications

(19 citation statements)

References 189 publications

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“…While the introduction of a ligand system that increases complex stability is a major achievement of this study; the other is that the obtained complexes [(DME) 4 •K][(DME)• RE(Cl) 2 {Si(SiMe 3 ) 2 SiMe 2 } 2 O] contain two chloride ligands. These provide the principal possibility to serve as entry points to a whole class of complexes, where the chlorides are replaced by all sorts of other anionic ligands.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…[(DME) 4 •K][(DME)•Dy(Cl) 2 {Si(SiMe 3 ) 2 SiMe 2 } 2 O] (2Dy). Following the general procedure, we used 1,3-bis[tris(trimethylsilyl)silyl]-1,1,3,3-tetramethyldisiloxane (151 mg, 0.24 mmol), potassium tertbutoxide (56 mg, 0.50 mmol), and dysprosium trichloride (69 mg, 0.26 mmol) in DME (2 mL).…”

Section: ■ Experimental Partmentioning

confidence: 99%

“…Observed NMR data were found to be in accordance with reported literature values. 16 [(DME) 4 •K][In(Cl) 2 {Si(SiMe 3 ) 2 SiMe 2 } 2 O] (4). A solution of compound 2Y (freshly prepared from tetrakis(trimethylsilyl)silyl]-1,1,3,3-tetramethyldisiloxane (150 mg, 0.24 mmol), potassium tertbutoxide (55 mg, 0.49 mmol), and yttrium trichloride (51 mg, 0.26 mmol)) in DME (1.5 mL) was added dropwise to indium trichloride (43 mg, 0.27 mmol) and stirred at room temperature under the exclusion of light for 135 min.…”

Section: ■ Experimental Partmentioning

confidence: 99%

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Rare-Earth–Silyl ate-Complexes Opening a Door to Selective Manipulations

2021

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The reactions of a number of rare-earth (RE) trichlorides and an oligosilanylene diide containing a siloxane unit in the backbone in DME are described. The formed products of the type [(DME) 4 ·K][(DME)·RE(Cl) 2 {Si(SiMe 3 ) 2 SiMe 2 } 2 O] (RE = Y, La, Ce, Pr, Sm, Tb, Dy, and Er) are disilylated dichloro metalate complexes and include the first examples of Si–La and Si–Pr compounds as well as the first structurally characterized example of a Si–Dy complex. A most intriguing aspect of the synthesis of these complexes is that they offer entry into a systematic study of the still largely unexplored field of silyl RE complexes by the possibility of ligand exchange reactions under preservation of the Si–RE interaction. This was demonstrated by the conversion of [(DME) 4 ·K][(DME)·RE(Cl) 2 {Si(SiMe 3 ) 2 SiMe 2 } 2 O] to [(DME) 4 ·K][Cp 2 Y{Si(SiMe 3 ) 2 SiMe 2 } 2 O].

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Experimental Partmentioning

confidence: 99%

Section: ■ Experimental Partmentioning

confidence: 99%

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Rare-Earth–Silyl ate-Complexes Opening a Door to Selective Manipulations

2021

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“…Most lanthanide elements, such as europium (Eu 3+ ) and terbium (Tb 3+ ), have unique luminescence performance, a high color purity, and a stable emission wavelength [ 1 , 2 , 3 , 4 , 5 , 6 ], so they are used in lasers and luminescent materials, as well as biomedical applications [ 7 , 8 , 9 , 10 , 11 , 12 ]. However, it is a fact that they emit relatively weak luminescence, so lanthanide ions (Ln 3+ ) have to be coordinated with organic ligands to form luminescence complexes to obtain better fluorescent properties [ 13 , 14 , 15 , 16 , 17 ].…”

Section: Introductionmentioning

confidence: 99%

Novel Cuboid-like Crystalline Complexes (CLCCs), Photon Emission, Fluorescent Fibers, and Bright Red Fabrics of Eu3+ Complexes Adjusted by Amphiphilic Molecules

Tang

Liu

et al. 2022

Polymers

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With the growing needs for flexible fluorescence emission materials, emission fibers and related wearable fabrics with bright emission properties have become key factors for wearable applications. In this article, novel cuboid-like crystals of Eu3+ complexes were generated. Except for light-energy-harvesting ligands of thenoyltrifluoroacetone (TTA) and 1,10-phenanthroline hydrate (Phen), the crystal structures were adjusted by other functional amphiphilic molecules. Not only does ETPC-SA, adjusted by stearic acid, have a regular cuboid-like crystal with a size of about 2 μm size, but it also generates the best photon emission property, with a fluorescence quantum yield of 98.4% fluorescence quantum yield in this report. Furthermore, we succeeded in producing novel fluorescent fibers by mini-twin-screw extrusion, and it was easy to form bright red fabrics, which are equipped with strong fluorescence intensity, flexibility, and a smooth hand feeling, with the normal fabricating method in our work. It is worth noting that ETPC-HQ fibers, which carry a crystal complex adjusted by hydroquinone, possess the lowest quantum yield but have the longest average fluorescence lifetime of 1259 µs. This result means that a low-density polyethylene (LDPE) matrix could make excited electrons stand in the excited state for a relatively long time when adjusted by hydroquinone, so as to increase the afterglow property of fluorescent fibers.

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“…32,33 In contrast, the high coordination numbers, kinetic lability, and very polar metal-ligand bonding of electrophilic lanthanide-organic complexes have proven effective in diverse heteroatom hydroelementation and polymerization processes. 34 These characteristics and the evidence that lanthanide catalysts frequently operate by entirely different reaction mechanisms than d-block catalysts 35 raise the intriguing question of whether they might activate pyridines via unusual and potentially useful reactivity modalities.…”

mentioning

confidence: 99%

Chemodivergent Organolanthanide Catalyzed C-H a-Mono-1 Borylation of Azines

Rothbaum¹,

Motta

Kratish³

et al. 2021

Preprint

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C-H activation and functionalization of pyridinoid azines is a key transformation forthe synthesis of many natural products, pharmaceuticals, and materials. Reflecting the azinyl nitrogen lone-pair steric repulsion, tendency to irreversibly bind to metal ion catalysts, and the electron-deficient nature of pyridine, C-H functionalization at the important a-position remains challenging. Thus, the development of earth abundant catalysts for the a-selective mono-functionalization of azines is a crucial hurdle for modern chemical synthesis. Here, the selective organolanthanide catalyzed a-mono-borylation of a diverse series of pyridines is reported, affording a valuable precursor for cross-coupling reactions. Experimental and theoretical mechanistic evidence support the formation of a C-H activated η2-lanthanide-azine complex, followed by intermolecular a-mono-borylation via σ-bond metathesis. Notably, varying the lanthanide identity and substrate electronics promotes chemodivergence of the catalytic selectivity: smaller/more electrophilic lanthanide3+ ions and electron-rich substrates favor selective a-C-H functionalization, whereas larger/less electrophilic lanthanide3+ 1 ions and electron poor substrates favor selective B-N bond-forming 1,2-dearomatization. Such organolanthanide series catalytic chemodivergence is, to our knowledge, unprecedented.

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Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2019

Cited by 24 publications

References 189 publications

Rare-Earth–Silyl ate-Complexes Opening a Door to Selective Manipulations

Rare-Earth–Silyl ate-Complexes Opening a Door to Selective Manipulations

Novel Cuboid-like Crystalline Complexes (CLCCs), Photon Emission, Fluorescent Fibers, and Bright Red Fabrics of Eu3+ Complexes Adjusted by Amphiphilic Molecules

Chemodivergent Organolanthanide Catalyzed C-H a-Mono-1 Borylation of Azines

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