Reactions of the spiro monoanion [{(Me2N)Sb(μ-NCy)2}2Sb]− with alcohols and thiols (REH; E = O or S); syntheses of nido-[Sb3(μ-NCy)3(μ3-NCy)(ER)2] anions and the unique antimony(III) imido cubane [(2-NC5H4O)Sb(μ3-NCy)]4 (Cy= cyclohexyl)

Bashall, Alan; Beswick, Michael A.; Feeder, Neil; Hopkins, Alexander D.; Kidd, Sara J.; McPartlin, Mary; Raithby, Paul R.; Wright, Dominic S.

doi:10.1039/b001322f

Cited by 7 publications

(3 citation statements)

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“…Compound 1 is a unique example of a mixed Li/Sb(III) amide complex. Heterobimetallic alkali metal/Sb(III) complexes with nitrogen ligands have been reported earlier, but these are exclusively imides ,, or mixed amide/imide compounds, , each with cage architectures. In 1 ·THF, the Sb–N separations within the central SbLiN 2 ring are 205.9(4) and 206.4(4) pm and therefore within the range of 198–216 pm in which other Sb–N(amide) bonds have been observed. − In contrast, the remaining two Sb–N contacts to the “exposed” Azn moieties (N3, N4) are markedly elongated to 222.8(8) and 224.0(4) pm, which fits to the trigonal bipyramidal coordination model.…”

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confidence: 94%

“…The coordination can be described as pseudotrigonal bipyramidal with N3 and N4 defining the axial positions (N3–Sb–N4 162.6(1)°). The distinct stereoactivity of the lone-pair is typical for antimony(III), − while in the case of the heavier homologue bismuth(III), various structures with a stereochemically inactive lone pair have been described. , One of the Li atoms in 1 ·THF (Li1) is part of a virtually planar SbLiN 2 ring and displays a tetrahedral coordination by the two ring Azn moieties and two Cl atoms. The two remaining Li atoms (Li2, Li3) are each part of a centrosymmetric Li 2 Cl 2 ring, where a tetrahedral coordination is completed by an Azn moiety and a THF ligand.…”

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Synthesis and Crystal Structures of the First Antimony(III) Aziridinides

et al. 2017

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The first antimony(III) aziridinyl derivatives are reported. Treatment of anhydrous SbCl with N-lithioaziridine Li(Azn) (Azn = NCH) afforded the structurally unique heterobimetallic lithium/antimony(III) amide complex [LiSb(μ-Cl)(μ-Azn)(THF)] (1). Homoleptic Sb(Azn) (2) has become available for the first time through an amide group exchange reaction between Sb(NMe) and 3 equiv of aziridine. The low-melting Sb(Azn) exhibits a "weak dimer" structure in the crystal.

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Synthesis and Crystal Structures of the First Antimony(III) Aziridinides

et al. 2017

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“…The presence of two different donor atoms results in rich coordination chemistry with a variety of potential binding modes for the oxypyridinato ligand, common examples of which are shown in Figure 2, illustrating the unusual binding modes of the {hp} ligand that constrained 1,3-N,O (four-membered ring) coordination can induce. A search of the literature reveals numerous oxypyridinato ligated transition metal complexes, whilst there are in comparison only a handful of main group complexes (reported in the CSCD) [70][71][72][73][74][75], and to date, none of these represent Sn(II)-supported species. In contrast, the quinolinato, {hq} and the oxybenzo[h]quinolinato {hbq} ligands exclusively display 1,4-and 1,5-κ 2 -N,O coordination modes, respectively.…”

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N-O Ligand Supported Stannylenes: Preparation, Crystal, and Molecular Structures

et al. 2022

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A new series of tin(II) complexes (1, 2, 4, and 5) were successfully synthesized by employing hydroxy functionalized pyridine ligands, specifically 2-hydroxypyridine (hpH), 8-hydroxyquinoline (hqH), and 10-hydroxybenzo[h]quinoline (hbqH) as stabilizing ligands. Complexes [Sn(μ-κ2ON-OC5H4N)(N{SiMe3}2)]2 (1) and [Sn4(μ-κ2ON-OC5H4N)6(κ1O-OC5H4N)2] (2) are the first structurally characterized examples of tin(II) oxypyridinato complexes exhibiting {Sn2(OCN)2} heterocyclic cores. As part of our study, 1H DOSY NMR experiments were undertaken using an external calibration curve (ECC) approach, with temperature-independent normalized diffusion coefficients, to determine the nature of oligomerisation of 2 in solution. An experimentally determined diffusion coefficient (298 K) of 6.87 × 10−10 m2 s−1 corresponds to a hydrodynamic radius of Ca. 4.95 Å. This is consistent with the observation of an averaged hydrodynamic radii and equilibria between dimeric [Sn{hp}2]2 and tetrameric [Sn{hp}2]4 species at 298 K. Testing this hypothesis, 1H DOSY NMR experiments were undertaken at regular intervals between 298 K–348 K and show a clear change in the calculated hydrodynamic radii form 4.95 Å (298 K) to 4.35 Å (348 K) consistent with a tetramer ⇄ dimer equilibria which lies towards the dimeric species at higher temperatures. Using these data, thermodynamic parameters for the equilibrium (ΔH° = 70.4 (±9.22) kJ mol−1, ΔS° = 259 (±29.5) J K−1 mol−1 and ΔG°298 = −6.97 (±12.7) kJ mol−1) were calculated. In the course of our studies, the Sn(II) oxo cluster, [Sn6(m3-O)6(OR)4:{Sn(II)(OR)2}2] (3) (R = C5H4N) was serendipitously isolated, and its molecular structure was determined by single-crystal X-ray diffraction analysis. However, attempts to characterise the complex by multinuclear NMR spectroscopy were thwarted by solubility issues, and attempts to synthesise 3 on a larger scale were unsuccessful. In contrast to the oligomeric structures observed for 1 and 2, single-crystal X-ray diffraction studies unambiguously establish the monomeric 4-coordinate solid-state structures of [Sn(κ2ON-OC9H6N)2)] (4) and [Sn(κ2ON-OC13H8N)2)] (5).

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Antimony: Inorganic ChemistryBased in part on the article Antimony: Inorganic Chemistry by R. Bruce King which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Breunig¹

2005

Encyclopedia of Inorganic Chemistry

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Reactions of the spiro monoanion [{(Me2N)Sb(μ-NCy)2}2Sb]− with alcohols and thiols (REH; E = O or S); syntheses of nido-[Sb3(μ-NCy)3(μ3-NCy)(ER)2] anions and the unique antimony(III) imido cubane [(2-NC5H4O)Sb(μ3-NCy)]4 (Cy= cyclohexyl)

Cited by 7 publications

References 26 publications

Synthesis and Crystal Structures of the First Antimony(III) Aziridinides

Synthesis and Crystal Structures of the First Antimony(III) Aziridinides

N-O Ligand Supported Stannylenes: Preparation, Crystal, and Molecular Structures

Antimony: Inorganic ChemistryBased in part on the article Antimony: Inorganic Chemistry by R. Bruce King which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

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