Synthesis and x‐ray crystal structures of hypervalent hexacoordinate antimony compounds without halogen ligands

Wakisaka, Yukiya; Yamamoto, Yohsuke; Akiba, Kin‐ya

doi:10.1002/1098-1071(2001)12:1<33::aid-hc7>3.0.co;2-#

Cited by 7 publications

(3 citation statements)

References 13 publications

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“…The primary coordination sphere of antimony in 1 is formed by the ipso carbon atom of the ligand L 1 , two chlorine atoms, and two moderately strongly coordinated oxygen donor atoms, with bond lengths Sb(1)−O(1) 2.577(2) Å and Sb(1)−O(2) 2.523(2) Å shorter than the sum of the van der Waals radii, ∑ vdW (Sb,O) = 3.78 Å . These values still indicate stronger Sb−O interaction than had been found in 2-[EtOC(CF 3 ) 2 ]C 6 H 4 Sb(2-OC(CF 3 ) 2 C 6 H 4 ) 8a. The overall geometry can be described as distorted square-pyramidal,17a where the ipso -carbon of L 1 is located in an apical position and Sb(1), O(1), O(2), Cl(1), and Cl(2) form the distorted basal plane (the sum of angles describing the SbO 2 Cl 2 girdle is 353.3°).…”

Section: Resultsmentioning

confidence: 80%

“…In contrast to the common occurrence of Sb−N or Bi−N intramolecular interactions only few examples of complexes with Sb−O or Bi−O intramolecular coordination have been reported. The presence of an Sb−O intramolecular interaction was found in compounds containing 2-[EtOC(CF 3 ) 2 ]C 6 H 4 - and [2-(OCH)C 6 H 4 ] - coordinating units . The intramolecular Bi−O contacts were established by X-ray crystallography in compounds bearing 2-( t BuSO 2 )C 6 H 4 - , 2-(OCMe)C 6 H 4 - , 2-(MeO)C 6 H 4 - , 2,6-(MeO) 2 C 6 H 3 - , 2-(MeOCMe 2 )C 6 H 4 - , and [2-MeOC(CF 3 ) 2 ]C 6 H 4 - 13 as ancillary ligands.…”

Section: Introductionmentioning

confidence: 96%

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Structural Diversity of Organoantimony(III) and Organobismuth(III) Dihalides Containing O,C,O-Chelating Ligands

et al. 2006

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Eight organoantimony and organobismuth dihalides, containing two types of O,C,O-chelating (so-called pincer) ligands, 2,6-(ROCH2)C6H3 - (R = Me, L1; R = t Bu, L2; L1SbCl2 (1), L2SbCl2 (2), L1SbI2 (3), L2SbI2 (4), L1BiCl2 (5), L2BiCl2 (6), L1BiI2 (7), L2BiI2 (8)) were prepared and characterized with the help of elemental analysis, electrospray ionization mass spectrometry, 1H and 13C NMR spectroscopy, and X-ray diffraction techniques. Except for 5, which exists as a centrosymmetric dimer, all studied compounds are monomeric in the solid state and the coordination polyhedra of the central atoms are distorted square-pyramidal. Both oxygen donor atoms are coordinated to the central metal through moderately strong or strong intramolecular interactions (range of Sb−O distances 2.279(2)−2.6912(14) Å and Bi−O distances 2.379(3)−2.460(4) Å), both in cis fashion for 1 and 2 (angles O−Sb−O 116.65(5)° and 116.73(4)°) and trans fashion for 3, 4, and 6−8 (range of angles O−M−O; M = Sb or Bi, 142.26(12)−148.28(8)°). In noncoordinating solvents (CDCl3, toluene-d 8) 1−8 display structures similar to those found in the solid state based on variable-temperature 1H NMR measurements.

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Section: Resultsmentioning

confidence: 80%

Section: Introductionmentioning

confidence: 96%

Structural Diversity of Organoantimony(III) and Organobismuth(III) Dihalides Containing O,C,O-Chelating Ligands

et al. 2006

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“…Yamamoto et al reported the first hypervalent organoantimony compound containing pendant-arm ligand 2-(Me 2 NCH 2 )C 6 H 4 in 1992 [40]. Almost all the hypervalent organoantimony compounds with intramolecular N Sb interaction reported so far are trivalent compounds, though a few pentavalent and monovalent compounds have also been reported [37,[41][42][43][44].…”

Section: Hypervalent Organoantimony Compounds With Intramolecular N Smentioning

confidence: 99%

Synthesis, Structure and Applications of Hypervalent Organoantimony Compounds Having Intramolecular E→Sb (E = N, O, S) Coordinations

Tan

Chen

Yin

et al. 2012

COC

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The review article covers the hypervalent organoantimony compounds that are with intramolecular N, O, S Sb coordinations synthesized in the past 20 years. We describe their structures and the related coordination chemistry, highlighting a number of hypervalent stibines. These compounds have shown many applications in organic synthesis. They are useful reagents for reactions such as crosscoupling and arylation with organic halides, and addition with carbonyl compounds. They can be used as Lewis acid catalysts in organic synthesis. Furthermore, they can be utilized as catalysts or reagents for CO2 chemical fixation. It is envisaged that more hypervalent organoantimony compounds of novel structure will be synthesized and find new applications in the near future.

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Stimuli‐Responsive Optical Materials Based on Hypervalent Antimony‐Containing Conjugated Molecules

Tanimura,

Gon,

Tanaka

et al. 2024

Adv Funct Materials

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Stimuli‐responsive materials have been applied for sensor devices because they can transform and amplify various target stimuli into observable signals. Much effort has been devoted to exploring effective molecular designs for obtaining stimuli‐responsive behaviors by taking advantage of the unique optoelectronic properties of π‐conjugated molecules involving various elements. This study focuses on the modulation of the electronic state of the π‐conjugated scaffolds by the oxidation number change of the hypervalent antimony. This study demonstrate that the strength of the intramolecular interaction between hypervalent antimony and the π‐conjugated framework can be tuned with ligand structure, substituent effect, and oxidation number shifts of hypervalent antimony. In particular, the color changes represented by hypsochromic and bathochromic wavelength shifts of optical bands are achieved by the oxidative reaction of hypervalent antimony in the solid state. Significantly, the direction of the color changes can be confidently predicted by quantum chemical calculations. The findings, based on the electronic interaction between π‐conjugated scaffolds and hypervalent main‐group elements, provide logical design strategies for advanced stimuli‐responsive materials.

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Synthesis and x‐ray crystal structures of hypervalent hexacoordinate antimony compounds without halogen ligands

Cited by 7 publications

References 13 publications

Structural Diversity of Organoantimony(III) and Organobismuth(III) Dihalides Containing O,C,O-Chelating Ligands

Structural Diversity of Organoantimony(III) and Organobismuth(III) Dihalides Containing O,C,O-Chelating Ligands

Synthesis, Structure and Applications of Hypervalent Organoantimony Compounds Having Intramolecular E→Sb (E = N, O, S) Coordinations

Stimuli‐Responsive Optical Materials Based on Hypervalent Antimony‐Containing Conjugated Molecules

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