Ligandenstabilisierte Chalkogendikationen

Chivers, Tristram; Konu, Jari

doi:10.1002/ange.200806010

Cited by 3 publications

(1 citation statement)

References 46 publications

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“…39 Use of aryl or secondary alkyl‐substituted diazabutadiene ligands should reduce the propensity for elimination of a side group. The isolation of the tellurium NHC analogue has been identified as a challenge,40 and in this context we now report the synthesis of dicationic Te II N‐heterocycles, by using a coordination/halide abstraction pathway, relying on a 2,2′‐bipyridine sequestered source of TeCl 2 . An alternate route, based on a diamine ligand allowed for isolation of a Te IV N‐heterocycle in a base‐stabilized form, representing the first isovalent and isostructural dicationic analogue of an N‐heterocyclic carbene.…”

Section: Introductionmentioning

confidence: 99%

Dicationic Tellurium Analogues of the Classic N‐Heterocyclic Carbene

Dutton

Ragogna

2010

Chemistry A European J

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The synthesis and comprehensive characterization of the first dicationic tellurium analogues of N-heterocyclic carbenes (NHCs) has been reported, in both the +2 and +4 oxidation states. For the +2 oxidation state, a base-stabilized form of TeCl(2) is used as the starting material. The dications are isolated by means of halide metathesis and the solid-state structures confirm the previously calculated diimine bonding arrangement. For Te(IV), a diamine is used in a high-yielding dehydrohalogen coupling reaction from TeCl(4). The dicationic NHC analogue is isolated in a base-stabilized form through halide abstraction and subsequent coordination by pyridine.

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Section: Introductionmentioning

confidence: 99%

Dicationic Tellurium Analogues of the Classic N‐Heterocyclic Carbene

Dutton

Ragogna

2010

Chemistry A European J

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The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure

Kaim

Sieger

Greulich

et al. 2010

Journal of Organometallic Chemistry

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Isolation of Homoleptic Dicationic Tellurium and Monocationic Bismuth Analogues of Non-N-Heterocyclic Carbene Derivatives

et al. 2020

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The first examples of Te analogues of non-N-heterocyclic carbene (non-NHC) derivatives, [(ppy)2Te]·2ClO4, [4]·2ClO4, and[(ppy)2Te]·2OTf, [5]·2OTf [where ppy = 2-(2′-pyridyl)phenyl and Tf = O2SCF3] are reported by the metathesis reaction of diorganoiodotelluronium(IV) cation, [(ppy)2TeI]·I3, [3]·I3, with AgClO4 and AgOTf, respectively. The metathesis reaction of ppyTeCl3, 6, with an excess of AgClO4 resulted in the isolation of [ppyTe(μ-O)]2·2ClO4, [8]·2ClO4. The reaction of triorganotelluronium(IV) cation [(ppy)3Te]·Br, [10]Br, with K2PdCl4 afforded [(ppy)2TeCl]·[(ppy)PdCl2], 11. The generality of the “ppy” group on stabilizing other main-group non-NHC analogues has been further established by synthesizing the second example of a Bi analogue of a non-NHC derivative, namely, bismuthenium ion, [(ppy)2Bi]·Cl, [12]·Cl, using the same aryl group. All of the synthesized compounds are unambiguously authenticated by single-crystal X-ray diffraction studies. DFT calculations [natural bond orbital (NBO), atoms in molecules (AIM), and electron localization function (ELF)] indicate that the stability of the non-NHC carbenoids relies on the σ-hole participation of the Te/Bi atom with the strong intramolecular coordination ability of the pyridyl N atom of the aryl substituent.

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Ligandenstabilisierte Chalkogendikationen

Cited by 3 publications

References 46 publications

Dicationic Tellurium Analogues of the Classic N‐Heterocyclic Carbene

Dicationic Tellurium Analogues of the Classic N‐Heterocyclic Carbene

The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure

Isolation of Homoleptic Dicationic Tellurium and Monocationic Bismuth Analogues of Non-N-Heterocyclic Carbene Derivatives

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