A sodium boroxide containing an unusual Na4O4 ladder core

Cole, Sarah C.; Coles, Martyn P.; Hitchcock, Peter B.

doi:10.1016/j.inoche.2010.06.039

Cited by 3 publications

(11 citation statements)

References 35 publications

(22 reference statements)

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“…In contrast, their boron-containing isoelectronic analogues (Scheme b) are elusive. On the other hand, boroxide ligands have been applied in coordination chemistry with different main group metals − and transition metals − and exhibited distinct catalytic properties. , Although hundreds of these species have been well investigated in their neutral form, the study of the structure of the corresponding reduced radical and anionic species is rare.…”

Section: Introductionmentioning

confidence: 99%

Diradical Anion of Potassium Aggregate: Reduction of Dimer Boroxide Complex

et al. 2018

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Crystalline aggregates containing metal cation clusters “wrapped” by reduced hydrocarbon anions have been presented. Initially, a dimeric complex (2) possessing a bimetallic K2O2 core was synthesized from the reaction between an anthracene substituted boronic acid (2-(anthracen-9-yl)phenyl)(hydroxy)(mesityl)borane (1-H) and KN(SiMe3)2 in THF solution. The B–O bond length (1.281(4) Å) in complex 2 is comparable to those observed in oxoboranes, indicating this may be a double bond, which is supported by its Wiberg bond order (1.9) predicted by density functional theory calculations. Subsequently, potassium aggregate complexes, diradical 3 and dihydro anion 4, were obtained through the reduction reactions of dimeric complex 2 and 1-H, respectively. They exhibit similar K3O2B2 aggregate structures, but differ significantly in the geometry of the anthracene units. Complex 3 features a triplet diradical character with planar anthracene units that carry the unpaired electrons, while the anthracene groups in complex 4 display a puckered structure due to the addition of hydrogen atoms.

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Section: Introductionmentioning

confidence: 99%

Diradical Anion of Potassium Aggregate: Reduction of Dimer Boroxide Complex

et al. 2018

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“…In the case of 4, a single set of aromatic resonances is observed, with a multiplet resonance comprising overlapping doublets observed for the diastereotopic methylene protons. A single resonance was observed for each compound in the 11 B NMR spectra at δ = 2.40 and 2.33 ppm, respectively. The upfield shift cf.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Amino-tris-phenoxy-boryloxy (A) and Amino-bisphenoxy-boryloxy Ligands (B) with Their Core Amine-Stabilized Boryloxy Unit Highlighted. studies were unsuccessful; however, 1 H, 11 B, and 13 C{ 1 H} NMR spectra showed the formation of a single, clean product. It was possible to obtain crystals of the analogous ethyl ester, 5 (see SI: Figure S1), upon dissolving 4 in ethanol, demonstrating the initial presence of 4.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Recrystallization from chloroform at −28 °C gave 0.390 g (39%) of pale-yellow crystals. Details of 1 H, 11…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…In addition to being more electron-poor than their boronic acid counterparts, borinic acids can also feature two bulky substituents (e.g., {Mes 2 BOH}), sterically stabilizing the resulting metal complex. Examples from across the periodic table are known, including, but not limited to, alkali metals, − early transition metals, − and group 12 , and group 14 − metals. (Figure B–D).…”

Section: Introductionmentioning

confidence: 99%

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Lithium, Tin(II), and Zinc Amino-Boryloxy Complexes: Synthesis and Characterization

et al. 2023

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Analogous to the ubiquitous alkoxide ligand, metal boroxide and boryloxy complexes are an underexplored class of hard anionic O − ligand. A new series of amine-stabilized Li, Sn(II), and Zn boryloxy complexes, comprising electron-rich tetrahedral boron centers have been synthesized and characterized. All complexes have been characterized by one-dimensional (1D), two-dimensional (2D), and DOSY NMR, which are consistent with the solid-state structures unambiguously determined via single-crystal X-ray diffraction. Electron-rich μ 2 -(Sn and Zn) and μ 3 -(Li) boryloxy binding modes are observed. Compounds 6−9 are the first complexes of this class, with the chelating bis-and trisphenol ligands providing a scaffold that can be easily functionalized and provides access to the boronic acid pro-ligand, hence allowing facile direct synthesis of the resulting compounds. Computational quantum chemical studies suggest a significant enhancement of the π-donor ability of the amine-stabilized boryloxy ligand because of electron donation from the amine functionality into the porbital of the boron atom.

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Metal compounds of boron-substituted alkoxide (‘boroxide’) ligands

Coles

2016

Coordination Chemistry Reviews

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A sodium boroxide containing an unusual Na4O4 ladder core

Cited by 3 publications

References 35 publications

Diradical Anion of Potassium Aggregate: Reduction of Dimer Boroxide Complex

Diradical Anion of Potassium Aggregate: Reduction of Dimer Boroxide Complex

Lithium, Tin(II), and Zinc Amino-Boryloxy Complexes: Synthesis and Characterization

Metal compounds of boron-substituted alkoxide (‘boroxide’) ligands

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