Low-coordinate first-row transition metal complexes in catalysis and small molecule activation

Taylor, Laurence J.; Kays, Deborah L.

doi:10.1039/c9dt02402f

Cited by 51 publications

(23 citation statements)

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“…One important example is the m-terphenyl ligand, which has been repeatedly utilised in the isolation of low-coordinate main group and transition metal complexes. [1][2][3][4][5][6] Although a plethora of m-terphenyl frameworks have been designed, most studies have been structurally focused, aimed at investigating the effects of steric bulk on the geometries, bonding modes, and reactivities of the resulting compounds. [7][8][9][10][11][12][13][14][15][16][17][18] For instance, the solid state structures observed for a series of m-terphenyl lithium complexes vary depending on the steric demands of the flanking ortho-aryl substituents.…”

Section: Introductionmentioning

confidence: 99%

Structural and electronic studies of substituted m-terphenyl lithium complexes

et al. 2021

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Section: Introductionmentioning

confidence: 99%

Structural and electronic studies of substituted m-terphenyl lithium complexes

et al. 2021

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“…650.00) showing its fragment at m/z = 254 to be highly stable (base peak). The other important mass fragments in their increasing abundance (%) were found as 650 (18) (42), and 781 (30). The base peaks of the metal complexes were found to be distinct in their m/z in relation to their ligand.…”

Section: Mass Spectramentioning

confidence: 92%

“…[ 29 ] The work emphasizes primarily on the pharmacology of those few compounds of first‐row transition metals that are cheaper, non‐toxic, and readily accessible for pharmacology. [ 30 ] In addition, these metal ions are the vital elements found in the biological intracellular atmosphere of living beings. [ 31 ] They are most abundantly found trace elements present in biological systems together with iron and most of the metalloproteins.…”

Section: Introductionmentioning

confidence: 99%

Design, facile synthesis, spectroscopic characterization, and medicinal probing of metal‐based new sulfonamide drugs: A theoretical and spectral study

Hassan

Sumrra

Raza

et al. 2020

Applied Organom Chemis

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Sulfonamide core‐based new ligands 4‐{[(2,4‐dihydroxyphenyl)methylidene]amino}benzene‐1‐sulfonamide as (L1) and 4‐[(2,4‐dihydroxyphenyl)methylidene]amino‐N‐(5‐methyl‐1,2‐oxazol‐3‐yl)benzene‐1‐sulfonamide as (L2) have been synthesized through condensation response and were characterized by their UV–Vis, FT‐IR, 1H NMR, 13C NMR, mass spectrometry, and elemental analyses. The ligands were reacted with transition metals (V, Fe, Co, Ni, Cu, and Zn) to synthesize the metal complexes (1)–(12). The metal complexes were also characterized, based on their physical (color, solubility, yield and melting point, conductance, magnetic), spectral (UV–Vis, FT‐IR, LC–MS), and microanalytical (elemental) data. The bidentate ligands were coordinated with transition metal salts by exploiting the azomethine nitrogen and the hydroxyl group oxygen. The electronic spectra for the metal complexes suggested them to have square‐pyramidal geometry for their vanadyl complexes whereas all the remaining complexes to be octahedral. The optimized geometries of the ligands at their ground state energies were studied through density functional approach at the B3LYP/6‐31G** level. The electronic, molecular electrostatic potential (MEP), and chemical descriptive properties were also explored by first‐principle insights. A clear intramolecular charge transfer was witnessed by occupied molecular orbitals (HOMO) to unoccupied molecular orbitals (LUMO). In addition, all the products were then tested for their antimicrobial potential against four bacterial (Staphylococcus aureus, Bacillus subtilis, Escherichia coli, and Klebsiella pneumoniae) and two fungal (Aspergillus flavus and Aspergillus niger) species. The synthetic products were also tested for their antioxidant and enzyme inhibition properties that gave the excellent results implying their bioactive nature. The screening results revealed the metal complexes to have enhanced bioactive actions in comparison with their respective ligands.

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“…Low-coordinate (often threecoordinate) complexes have been longstanding goals for synthetic work as they usually possess high reactivity as well as interesting properties. [2][3][4][5][6][7] Notably, three-coordinate Cu II carba-zolides were proposed by Fu and Jones as reactive intermediates in photoinduced Ullmann CÀ N coupling reactions which were observed by EPR spectroscopy after irradiation of Cu I carbazolides in the presence of iodobenzene. [5] However, all attempts to isolate this Cu II carbazolide failed as it rapidly decomposed in solution.…”

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Towards Heteroleptic Dicoordinate Cu^II Complexes

Kaiser

Göttlicher

Vitova

et al. 2021

Chemistry A European J

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In this work we detail our efforts to systematically generate stable dicoordinate Cu II complexes. Initial experiments via metathesis reactions of a bulky potassium carbazolide (RK) with copper(II) salts indeed yielded a stable product, RCuOTf (1). However, subsequent attempts to grasp systematic synthetic access to complexes of the type RCuX (X = monoanionic ligand) proved difficult as many of the complexes rapidly decomposed in solution. By using triflate-related ligands such as ethyl sulfate and bistriflimide, the additional dicoordinate copper complexes RCuOSO 3 Et (2), [RCu(THF)][Cu(NTf 2 ) 2 ] (3) and RCuNTf 2 (4) could be isolated. Spectroscopic indications corroborate more Cu I than Cu II character in all RCuX derivatives.

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Low-coordinate first-row transition metal complexes in catalysis and small molecule activation

Abstract: In this Perspective, we will highlight selected examples of transition metal complexes with low coordination numbers whose high reactivity has been exploited in catalysis and the activation of small molecules featuring strong bonds (N2, CO2, and CO).

Cited by 51 publications

References 142 publications

Structural and electronic studies of substituted m-terphenyl lithium complexes

Structural and electronic studies of substituted m-terphenyl lithium complexes

Design, facile synthesis, spectroscopic characterization, and medicinal probing of metal‐based new sulfonamide drugs: A theoretical and spectral study

Towards Heteroleptic Dicoordinate Cu^II Complexes

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Low-coordinate first-row transition metal complexes in catalysis and small molecule activation

Abstract: In this Perspective, we will highlight selected examples of transition metal complexes with low coordination numbers whose high reactivity has been exploited in catalysis and the activation of small molecules featuring strong bonds (N2, CO2, and CO).

Cited by 51 publications

References 142 publications

Structural and electronic studies of substituted m-terphenyl lithium complexes

Structural and electronic studies of substituted m-terphenyl lithium complexes

Design, facile synthesis, spectroscopic characterization, and medicinal probing of metal‐based new sulfonamide drugs: A theoretical and spectral study

Towards Heteroleptic Dicoordinate CuII Complexes

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Towards Heteroleptic Dicoordinate Cu^II Complexes