Telluronium Ions as σ‐Acceptor Ligands

Lin, Tzu‐Pin; Gabbaı̈, François P.

doi:10.1002/ange.201300337

Cited by 5 publications

(1 citation statement)

References 61 publications

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“…To compare the structural parameters of the diorganodications [ 4 ]·2ClO 4 and [ 5 ]·2OTf with the corresponding monocation (ppy) 3 Te + and to explore the coordination ability of the Te center, ppyBr, 9 , was treated with n BuLi followed by TeCl 4 to afford [(ppy) 3 Te]·Br, [ 10 ]·Br (Scheme ). Compound [ 10 ]·Br showed 125 Te NMR resonance at 867 ppm, which is consistent with the value observed for similar reported triorganotelluronium(IV) cations, namely, triphenyltelluronium chloride (773 ppm) and tris(8-quinolinyl)telluronium chloride (669 ppm) . Interestingly, when [ 10 ]·Br was treated with K 2 PdCl 4 , a reverse transmetalation was observed, resulting in the formation of the Pd II complex of chlorotelluronium cation, namely, [(ppy) 2 TeCl]·[(ppy)PdCl 2 ], 11 .…”

Section: Resultssupporting

confidence: 84%

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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Section: Resultssupporting

confidence: 84%

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

et al. 2020

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Evidence for C−F Bond Formation through Formal Reductive Elimination from Tellurium(VI)

et al. 2022

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The fundamental challenge of CÀ F bond formation by reductive elimination has been met by compounds of select transition metals and fewer main group elements. The work detailed herein expands the list of main group elements known to be capable of reductively eliminating a CÀ F bond to include tellurium. Surprising and novel modes of both sp 2 and sp 3 CÀ F bond formation were observed alongside formation of Te IV cations during two separate attempts to synthesize/ characterize fluorinated organotellurium(VI) cations in superacidic media (SbF 5 /SO 2 ClF). Following detailed low-temperature NMR experiments, the mechanisms of the two unique reductive elimination reactions were probed and investigated using density functional theory (DFT) calculations. Ultimately, we found that an "indirect" reductive elimination pathway is likely operative whereby Sb plays a key role in fluoride abstraction and CÀ F bond formation, as opposed to unimolecular reductive elimination from a discrete Te VI cation.

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Evidence for C−F Bond Formation through Formal Reductive Elimination from Tellurium(VI)

et al. 2022

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The fundamental challenge of C−F bond formation by reductive elimination has been met by compounds of select transition metals and fewer main group elements. The work detailed herein expands the list of main group elements known to be capable of reductively eliminating a C−F bond to include tellurium. Surprising and novel modes of both sp2 and sp3 C−F bond formation were observed alongside formation of TeIV cations during two separate attempts to synthesize/characterize fluorinated organotellurium(VI) cations in superacidic media (SbF5/SO2ClF). Following detailed low‐temperature NMR experiments, the mechanisms of the two unique reductive elimination reactions were probed and investigated using density functional theory (DFT) calculations. Ultimately, we found that an “indirect” reductive elimination pathway is likely operative whereby Sb plays a key role in fluoride abstraction and C−F bond formation, as opposed to unimolecular reductive elimination from a discrete TeVI cation.

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Telluronium Ions as σ‐Acceptor Ligands

Cited by 5 publications

References 61 publications

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

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

Evidence for C−F Bond Formation through Formal Reductive Elimination from Tellurium(VI)

Evidence for C−F Bond Formation through Formal Reductive Elimination from Tellurium(VI)

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