Triethylantimony(V) complexes with bidentate O,N-, O,O- and tridentate O,N,O′-coordinating o-iminoquinonato/o-quinonato ligands: Synthesis, structure and some properties

Poddel’sky, Andrey I.; Vavilina, N. N.; Сомов, Н. В.; Cherkasov, V. K.; Abakumov, G. A.

doi:10.1016/j.jorganchem.2009.06.027

Cited by 36 publications

(18 citation statements)

References 44 publications

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“…Again, two tert-butyl resonances and two aromatic proton resonances are observed in the 1 H NMR spectrum, which indicate mirror plane symmetry in the complex, consistent with the structure depicted in Scheme 2 in which the (ONHO) 2-ligand is folded along the N-Zr bond to give an overall C s -symmetric structure. [21,22] Exposure of solutions of 2 to air resulted in a rapid color change from pale yellow to forest green, consistent with oxidation of the [ONO] ligand. When a suspension of 2 in benzene was treated with one equivalent of dry O 2 , the solid dissolved to produce a forest green solution.…”

Section: Resultsmentioning

confidence: 83%

A Redox‐Active Ligand as a Reservoir for Protons and Electrons: O₂ Reduction at Zirconium(IV)

Zarkesh

Heyduk

2011

Eur J Inorg Chem

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The [ONO] ligand {(ONOcat)3– = bis(3,5‐di‐tert‐butyl‐2‐phenoxy)amide} can be installed onto zirconium(IV) in two different protonation states. The reaction of (ONOcat)3– with ZrCl4 afforded the octahedral complex (ONOcat)ZrCl(THF)2 (1). This complex, characterized in the solid state by single‐crystal X‐ray diffraction and in solution by NMR,UV/Vis, and IR spectroscopy, is assigned as a zirconium(IV) complex coordinated to the fully reduced form of the [ONO] redox‐active ligand. When (ONOcat)H3 was doubly deprotonated and treated with ZrCl4, the complex (ONHO)ZrCl2(THF) (2) was isolated, in which one ligand proton remains on the [ONO] ligand. Exposure of 2 to dry O2 resulted in a four‐electron, two‐proton reaction to form the bis(hydroxo) complex [(ONOq)ZrCl2(μ‐OH)]2 (3), which shows that the [ONO] ligand platform can serve as both an electron and proton reservoir in small‐molecule reactions.

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Section: Resultsmentioning

confidence: 83%

A Redox‐Active Ligand as a Reservoir for Protons and Electrons: O₂ Reduction at Zirconium(IV)

Zarkesh

Heyduk

2011

Eur J Inorg Chem

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“…In contrast to the transition metals, the O 2 binding does not lead to a change in the antimony oxidation state, while the redox active ligand is involved in the redox reaction. The nature of functional groups in redox active ligands [ 65 , 66 , 67 , 68 ], as well as in substituents at a central antimony atom [ 69 , 70 , 71 , 72 , 73 , 74 ], affects the redox properties of antimony catecholates and their antioxidant activity [ 75 , 76 , 77 , 78 , 79 , 80 ]. Electron-donating groups in catecholate or at the antimony atom in complexes of the type CatSbR 3 shift the oxidation potential to the anodic region.…”

Section: Introductionmentioning

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

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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.

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“…Prepared initially as a binding fragment for heavy main group metals by Stegmann and Scheffler, [11][12][13] compound A exhibits a rich chelating chemistry for diverse transition metal and main group elements. [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] Chief among the findings in such studies is the propensity of the ONO fragment to support several discrete redox states as depicted in Figure 1: closed-shell trianionic A, open-shell dianionic semiquinonate B, and monoanionic quinonate C. Access to each of these electronic states may be controlled not only on the identity of the chelated element, but also by external reagents in such a way as to permit catalysis involving reversible interconversion of several or all of these electronic configurations. 30 We have been investigating the chemistry of phosphorus compounds supported within heteroatom-based trianionic binding motifs.…”

Section: Introductionmentioning

confidence: 99%

Stable Open-Shell Phosphorane Based on a Redox-Active Amidodiphenoxide Scaffold

Pistner¹,

Moon

Silakov³

et al. 2017

Inorg. Chem.

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The synthesis and redox reactivity of pentacoordinate phosphorus compounds incorporating a redox-active ONO amidodiphenoxide scaffold [ONO = N,N-bis(3,5-di-tert-butyl-2-phenoxide)amide] are described. Dichloro- and diphenylphosphoranes, 2·Cl and 2·Ph, respectively, are synthesized and crystallographically characterized. Cyclic voltammograms of 2·Cl show only a single irreversible oxidation (E = +0.83 V vs CpFe), while the diphenyl analogue 2·Ph is reversibly oxidized at lower applied potential (E = +0.47 V vs CpFe). Chemical oxidation of 2·Ph with AgBF produces the corresponding radical cation [2·Ph], where electron paramagnetic resonance spectroscopy and density functional theory calculations reveal that the unpaired spin density is largely ligand-based and is highly delocalized throughout the ONO framework of the paramagnetic species. The solid-state structures indicate only minor geometrical changes between the neutral 2·Ph and oxidized [2·Ph] species, consistent with fast self-exchange electron transfer, as observed by NMR line-broadening experiments.

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Triethylantimony(V) complexes with bidentate O,N-, O,O- and tridentate O,N,O′-coordinating o-iminoquinonato/o-quinonato ligands: Synthesis, structure and some properties

Cited by 36 publications

References 44 publications

A Redox‐Active Ligand as a Reservoir for Protons and Electrons: O₂ Reduction at Zirconium(IV)

A Redox‐Active Ligand as a Reservoir for Protons and Electrons: O₂ Reduction at Zirconium(IV)

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

Stable Open-Shell Phosphorane Based on a Redox-Active Amidodiphenoxide Scaffold

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Triethylantimony(V) complexes with bidentate O,N-, O,O- and tridentate O,N,O′-coordinating o-iminoquinonato/o-quinonato ligands: Synthesis, structure and some properties

Cited by 36 publications

References 44 publications

A Redox‐Active Ligand as a Reservoir for Protons and Electrons: O2 Reduction at Zirconium(IV)

A Redox‐Active Ligand as a Reservoir for Protons and Electrons: O2 Reduction at Zirconium(IV)

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

Stable Open-Shell Phosphorane Based on a Redox-Active Amidodiphenoxide Scaffold

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A Redox‐Active Ligand as a Reservoir for Protons and Electrons: O₂ Reduction at Zirconium(IV)

A Redox‐Active Ligand as a Reservoir for Protons and Electrons: O₂ Reduction at Zirconium(IV)