Triaryl/trialkylantimony(V) catecholates with electron-acceptor groups

Poddel’sky, Andrey I.; Smolyaninov, I. V.; Берберова, Н. Т.; Fukin, Georgy K.; Cherkasov, V. K.; Abakumov, G. A.

doi:10.1016/j.jorganchem.2015.04.045

Cited by 24 publications

(7 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These changes indicate the generation of an unstable dicationic intermediate [(Q)SbPh 3 ] 2+ in the near-electrode region. Earlier, we observed a similar electrochemical activity for the triphenylantimony(V) catecholates containing electron-withdrawing groups in the catecholate cycle, but in most cases, the dicationic derivatives formed in the electrooxidation were unstable [90,91]. The second wide quasi-reversible oxidation peak at 1.24 V is single electron in nature.…”

Section: Electrochemistrysupporting

confidence: 54%

“…A double increase in the current of the second oxidation peak as compared to the first one indicates an increase in the number of electrons involved in this electrode process to two. The value of the peak potential E ox2 p = 1.39 V on the CV of 1 is fixed in the potential range of 1.37-1.60 V, which is characteristic of the second redox process "o-semiquinone / o-benzoquinone" in such The value of the peak potential E ox2 p = 1.39 V on the CV of 1 is fixed in the potential range of 1.37-1.60 V, which is characteristic of the second redox process "o-semiquinone/o-benzoquinone" in such triarylantimony(V) catecholates [89][90][91]. This electrochemical picture in the case of 1 indicates the convergence of the boundary redox orbitals of o-semiquinone and phenolic fragments in 1 + , which leads to their simultaneous electrooxidation.…”

Section: Electrochemistrymentioning

confidence: 99%

“…the triphenylantimony(V) catecholates containing electron-withdrawing groups in the catecholate cycle, but in most cases, the dicationic derivatives formed in the electrooxidation were unstable [90,91]. The second wide quasi-reversible oxidation peak at 1.24 V is single electron in nature.…”

Section: Electrochemistrymentioning

confidence: 99%

See 2 more Smart Citations

Polyfunctional Sterically Hindered Catechols with Additional Phenolic Group and Their Triphenylantimony(V) Catecholates: Synthesis, Structure, and Redox Properties

et al. 2020

View full text Add to dashboard Cite

New polyfunctional sterically hindered 3,5-di-tert-butylcatechols with an additional phenolic group in the sixth position connected by a bridging sulfur atom—(6-(CH2-S-tBu2Phenol)-3,5-DBCat)H2 (L1), (6-(S-tBu2Phenol)-3,5-DBCat)H2 (L2), and (6-(S-Phenol)-3,5-DBCat)H2 (L3) (3,5-DBCat is dianion 3,5-di-tert-butylcatecolate)—were synthesized and characterized in detail. The exchange reaction between catechols L1 and L3 with triphenylantimony(V) dibromide in the presence of triethylamine leads to the corresponding triphenylantimony(V) catecholates (6-(CH2-S-tBu2Phenol)-3,5-DBCat)SbPh3 (1) and (6-(S-Phenol)-3,5-DBCat)SbPh3 (2). The electrochemical properties of catechols L1–L3 and catecholates 1 and 2 were investigated using cyclic voltammetry. The electrochemical oxidation of L1–L3 at the first stage proceeds with the formation of the corresponding o-benzoquinones. The second process is the oxidation of the phenolic moiety. Complexes 1 and 2 significantly expand their redox capabilities, owing to the fact that they can act as the electron donors due to the catecholate metallocycle capable of sequential oxidations, and as donors of the hydrogen atoms, thus forming a stable phenoxyl radical. The molecular structures of the free ligand L1 and complex 1 in the crystal state were determined by single-crystal X-ray analysis.

show abstract

Section: Electrochemistrysupporting

confidence: 54%

Section: Electrochemistrymentioning

confidence: 99%

See 1 more Smart Citation

Polyfunctional Sterically Hindered Catechols with Additional Phenolic Group and Their Triphenylantimony(V) Catecholates: Synthesis, Structure, and Redox Properties

et al. 2020

View full text Add to dashboard Cite

show abstract

“…The parameter τ = 0 in an ideal tetragonal pyramid; τ = 1 in an ideal trigonal bipyramid [ 84 ]. The geometric characteristics of redox-active O,O’-chelating ligands (such as the distances of oxygen-carbon bonds O(1)-C(1) and O(2)-C(2) and carbon-carbon bonds in a six-membered carbon cycle С(1-6)) correspond to the single oxygen-carbon bonds in catecholato complexes of antimony [ 85 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 , 96 ] and other metals [ 97 , 98 , 99 , 100 , 101 , 102 ].…”

Section: Resultsmentioning

confidence: 99%

Triphenylantimony(V) Catecholates of the Type (3-RS-4,6-DBCat)SbPh3-Catechol Thioether Derivatives: Structure, Electrochemical Properties, and Antiradical Activity

et al. 2021

View full text Add to dashboard Cite

A new series of triphenylantimony(V) 3-alkylthio/arylthio-substituted 4,6-di-tert-butylcatecholates of the type (3-RS-4,6-DBCat)SbPh3, where R = n-butyl (1), n-hexyl (2), n-octyl (3), cyclopentyl (4), cyclohexyl (5), benzyl (6), phenyl (7), and naphthyl-2 (8), were synthesized from the corresponding catechol thioethers and Ph3SbBr2 in the presence of a base. The crystal structures of 1, 2, 3, and 5 were determined by single-crystal X-ray analysis. The coordination polyhedron of 1–3 is better described as a tetragonal pyramid with a different degree of distortion, while that for 5- was a distorted trigonal bipyramid (τ = 0.014, 0.177, 0.26, 0.56, respectively). Complexes demonstrated different crystal packing of molecules. The electrochemical oxidation of the complexes involved the catecholate group as well as the thioether linker. The introduction of a thioether fragment into the aromatic ring of catechol ligand led to a shift in the potential of the “catechol/o-semiquinone” redox transition to the anodic region, which indicated the electron-withdrawing nature of the RS group. The radical scavenging activity of the complexes was determined in the reaction with DPPH radical.

show abstract

“…Nickel phosphine compounds have been studied for their catalytic properties for decades, and they are associated with a variety of catalytic reactions such as hydrogen production, hydrocyanation, and oligomerization . In an effort to better comprehend and optimize catalysis, phosphine ligands and their corresponding organic substituents have been studied for both steric and electronic effects. , Concerning heavier phosphorus group ligands, there have been studies on the relative steric and electronic effects in stand-alone antimony molecules, , but there are few extensive studies regarding the steric, electronic, magnetic, and spectroscopic properties of antimony–nickel (or other 3 d metal) complexes. − Such studies would provide a base of understanding for the design and synthesis of functional antimony-based complexes. Indeed, antimony ligands have proven to be effective donors to metal centers under certain conditions, , and productive catalysts that utilize antimony ligands have already been reported. − …”

Section: Introductionmentioning

confidence: 99%

Syntheses, Structures, and Characterization of Nickel(II) Stibines: Steric and Electronic Rationale for Metal Deposition

et al. 2018

View full text Add to dashboard Cite

Reactions of the homoleptic and heteroleptic antimony ligands Sb Pr, Sb PrPh, SbMePh, and SbMePh with NiI generate rare Ni stibine complexes in either square planar or trigonal bipyramidal (TBP) geometries, depending on the steric size of the ligands. Tolman electronic parameters were calculated (DFT) for each antimony ligand to provide a tabulated resource for the relative strengths of simple antimony ligands. The electronic absorbance spectra of the square planar complexes exhibit characteristic bands [λ ≈ 560 nm (17 900 cm), ε ≈ 4330 M cm] at lower energies compared to the reported phosphine complexes, indicating the weak donor strength of the stibine ligands and resultant low-energy ligand field d→ d transitions. The square planar complex Ni(I)(Sb Pr) reacts with CO to form the TBP complex Ni(I)(Sb Pr)(CO). Lastly, the complexes were investigated for nickel metal deposition on Si|Cu(100 nm) substrates. The complexes with the strongest donating ligand, Sb Pr, deposited the purest layer of NiCu alloy according to the balanced reaction Ni(I)(SbPr) → Ni + Sb( Pr)I; the iodinated Sb byproduct was unambiguously detected in the supernatant by H NMR and mass spectrometry. Complexes with weaker ligands (poor I acceptors/scavengers) resulted undesired deposition of iodine and CuI on the surface. This work thus serves as a guide for the design and synthesis of 3 d metal complexes with neutral, heavy main-group donors that are useful for metal deposition applications.

show abstract

Triaryl/trialkylantimony(V) catecholates with electron-acceptor groups

Cited by 24 publications

References 25 publications

Polyfunctional Sterically Hindered Catechols with Additional Phenolic Group and Their Triphenylantimony(V) Catecholates: Synthesis, Structure, and Redox Properties

Polyfunctional Sterically Hindered Catechols with Additional Phenolic Group and Their Triphenylantimony(V) Catecholates: Synthesis, Structure, and Redox Properties

Triphenylantimony(V) Catecholates of the Type (3-RS-4,6-DBCat)SbPh3-Catechol Thioether Derivatives: Structure, Electrochemical Properties, and Antiradical Activity

Syntheses, Structures, and Characterization of Nickel(II) Stibines: Steric and Electronic Rationale for Metal Deposition

Contact Info

Product

Resources

About