Hybrid Quinoline Telluroether Ligand Derived Copper and Silver Complexes: Synthesis, Structural and Electronic Properties

Raju, Saravanan; Singh, Harkesh B.; Kumar, Sangit

doi:10.1002/ejic.202200300

Cited by 3 publications

(1 citation statement)

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“…125 Te and 199 Hg NMR spectra of macrocycles 3 , 5 and metal complexes 6 and 7 show significant changes in chemical shift values while comparing with the related reported complexes [16d,25,28a–c] . For illustration, the 125 Te NMR spectrum of macrocycle 5 showed signal at δ 469 ppm and half cycle 3 exhibited (δ 496 ppm) where Hg is bonded with bromine.…”

Section: Resultsmentioning

confidence: 84%

Coordination Behavior of the Tellurium Incorporated Mercuraazametallamacrocycle and Investigation of d¹⁰⋅⋅⋅d¹⁰ Interactions between Closed Shell (Ag⁺ Hg²⁺) Metal Ions

Raju

Singh

Kumar

et al. 2023

Chemistry A European J

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Herein, a new tellurium and mercury containing mercuraazametallamacrocycle has been prepared via (2+2) condensation of bis(o‐aminophenyl)telluride and bis(o‐formylphenyl)mercury(II). The isolated bright yellow solid of mercuraazametallamacrocycle has adopted unsymmetrical figure‐of‐eight conformation in the crystal structure. To study the metallophilic interactions between closed shell metal ions, the macrocyclic ligand has been treated with two equiv. of AgOTf (OTf=trifluoromethansulfonate) and AgBF4, which afforded greenish‐yellow bimetallic silver complexes. The isolated silver complexes displayed intramolecular Hg⋅⋅⋅Ag, Te⋅⋅⋅Ag interactions as well as intermolecular Hg⋅⋅⋅Hg interactions and formed an extended 1D molecular chain by directing six atoms to interact as TeII⋅⋅⋅AgI⋅⋅⋅HgII⋅⋅⋅HgII⋅⋅⋅AgI⋅⋅⋅TeII in a non linear fashion. The Hg⋅⋅⋅Ag, Te⋅⋅⋅Ag interactions have also been studied in solution by 199Hg, 125Te NMR spectroscopy, absorption, and emission spectroscopy. In DFT calculations, the Atom in Molecule (AIM) analysis, non‐covalent interactions (NCI), natural bonding orbital (NBO) analysis strongly supported for experimental evidences and revealed that the intermolecular Hg⋅⋅⋅Hg interaction is stronger than the intramolecular Hg⋅⋅⋅Ag interactions.

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Section: Resultsmentioning

confidence: 84%

Coordination Behavior of the Tellurium Incorporated Mercuraazametallamacrocycle and Investigation of d¹⁰⋅⋅⋅d¹⁰ Interactions between Closed Shell (Ag⁺ Hg²⁺) Metal Ions

Raju

Singh

Kumar

et al. 2023

Chemistry A European J

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Pushing the Boundary of Covalency in Lanthanoid‐Tellurium Bonds: Insights from the Synthesis, Molecular and Electronic Structures of Low‐Coordinate, Monomeric Europium(II) and Ytterbium(II) Tellurolates

Deka

Dey

Guo

et al. 2023

Chemistry A European J

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Owing to the strict hard/soft dichotomy between the lanthanoids and tellurium atoms, and the strong affinity of lanthanoid ions for high coordination numbers, low‐coordinate, monomeric lanthanoid tellurolate complexes have remained elusive as compared to the lanthanoid complexes with lighter group 16 elements (O, S, and Se). This makes the development of suitable ligand systems for low‐coordinate, monomeric lanthanoid tellurolate complexes an appealing endeavor. In a first report, a series of low‐coordinate, monomeric lanthanoid (Yb, Eu) tellurolate complexes were synthesized by utilizing hybrid organotellurolate ligands containing N‐donor pendant arms. The reaction of bis[2‐((dimethylamino)methyl)phenyl] ditelluride, 1 and 8,8′diquinolinyl ditelluride, 2 with Ln0 metals (Ln=Eu, Yb) resulted in the formation of monomeric complexes [LnII(TeR)2(Solv)2] [R=C6H4‐2‐CH2NMe2] [3: Ln=Eu, Solv=tetrahydrofuran; 4: Ln=Eu, Solv=acetonitrile; 5: Ln=Yb, Solv=tetrahydrofuran; 6: Ln=Yb, Solv=pyridine] and [EuII(TeNC9H6)2(Solv)n] (7: Solv=tetrahydrofuran, n=3; 8: Solv=1,2‐dimethoxyethane, n=2), respectively. Complexes 3–4 and 7–8 represent the first sets of examples of monomeric europium tellurolate complexes. The molecular structures of complexes 3–8 are validated by single–crystal X‐ray diffraction studies. The electronic structures of these complexes were investigated using Density Functional Theory (DFT) calculations, which revealed appreciable covalency between the tellurolate ligands and lanthanoids.

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PIFA/Ar₂Te₂‐Mediated Synthesis of 3‐Aryltelluroindoles via Intramolecular Cyclization of 2‐Alkynylanilines

Zhang,

Yu,

Shi

et al. 2024

Eur J Org Chem

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The reaction of 2‐alkynylanilines with phenyliodonium bis(trifluoroacetate) (PIFA) and diaryl ditellurides was found to conveniently afford the corresponding 3‐aryltelluroindoles via oxidative cyclization/tellurolation. A plausible mechanism involving the in situ formation of the reactive ArTeOCOCF3 from the reaction of PIFA and diaryl ditellurides, and the subsequent oxidative C‐N/C‐Te bond formations was postulated.

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Hybrid Quinoline Telluroether Ligand Derived Copper and Silver Complexes: Synthesis, Structural and Electronic Properties

Cited by 3 publications

References 69 publications

Coordination Behavior of the Tellurium Incorporated Mercuraazametallamacrocycle and Investigation of d¹⁰⋅⋅⋅d¹⁰ Interactions between Closed Shell (Ag⁺ Hg²⁺) Metal Ions

Coordination Behavior of the Tellurium Incorporated Mercuraazametallamacrocycle and Investigation of d¹⁰⋅⋅⋅d¹⁰ Interactions between Closed Shell (Ag⁺ Hg²⁺) Metal Ions

Pushing the Boundary of Covalency in Lanthanoid‐Tellurium Bonds: Insights from the Synthesis, Molecular and Electronic Structures of Low‐Coordinate, Monomeric Europium(II) and Ytterbium(II) Tellurolates

PIFA/Ar₂Te₂‐Mediated Synthesis of 3‐Aryltelluroindoles via Intramolecular Cyclization of 2‐Alkynylanilines

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Hybrid Quinoline Telluroether Ligand Derived Copper and Silver Complexes: Synthesis, Structural and Electronic Properties

Cited by 3 publications

References 69 publications

Coordination Behavior of the Tellurium Incorporated Mercuraazametallamacrocycle and Investigation of d10⋅⋅⋅d10 Interactions between Closed Shell (Ag+ Hg2+) Metal Ions

Coordination Behavior of the Tellurium Incorporated Mercuraazametallamacrocycle and Investigation of d10⋅⋅⋅d10 Interactions between Closed Shell (Ag+ Hg2+) Metal Ions

Pushing the Boundary of Covalency in Lanthanoid‐Tellurium Bonds: Insights from the Synthesis, Molecular and Electronic Structures of Low‐Coordinate, Monomeric Europium(II) and Ytterbium(II) Tellurolates

PIFA/Ar2Te2‐Mediated Synthesis of 3‐Aryltelluroindoles via Intramolecular Cyclization of 2‐Alkynylanilines

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Coordination Behavior of the Tellurium Incorporated Mercuraazametallamacrocycle and Investigation of d¹⁰⋅⋅⋅d¹⁰ Interactions between Closed Shell (Ag⁺ Hg²⁺) Metal Ions

Coordination Behavior of the Tellurium Incorporated Mercuraazametallamacrocycle and Investigation of d¹⁰⋅⋅⋅d¹⁰ Interactions between Closed Shell (Ag⁺ Hg²⁺) Metal Ions

PIFA/Ar₂Te₂‐Mediated Synthesis of 3‐Aryltelluroindoles via Intramolecular Cyclization of 2‐Alkynylanilines