Experimental evidence for hypercoordination in triorganotelluronium halides with 2-(Me2NCH2)C6H4 groups

Beleaga, Anca; Denes, Eleonora; Silvestru, Cristian; Silvestru, Anca

doi:10.1039/c9nj02530h

Cited by 3 publications

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References 43 publications

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“…7 The [R 3 Te] + cations bearing three equivalent organic groups capable for a C,N chelating behaviour, e.g. tris[2-(2′-pyridyl)phenyl] telluronium bromide, 8 tris(8-quinolinyl)telluronium chloride, 9 and tris(N,N-dimethylbenzylamino)telluronium halides, 10 exhibit octahedral coordination geometries, thus enabling no further secondary bonding interactions between tellurium and X − anions. By contrast, in triphenyltelluronium halides 11 or pseudohalides 12 the anions behave as bridging units between neighbour tellurium atoms, thus increasing the coordination number at tellurium and resulting in dimeric or polymeric associations.…”

Section: Introduction *mentioning

confidence: 99%

New hypercoordinated triaryltelluronium derivatives of oraganophosphorus ligands. Synthesis and structural characterization

Denes¹,

Vlassa²,

Silvestru³

et al. 2021

Rev.Roum.Chim.

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Hypercoordinated triaryltelluronium compounds of type [{2-(Me2NCH2)C6H4}3Te]+L [L = (SPMe2)2N (1), (OPPh2)2N (2), (SPPh2)2N (3), (SPPh2){OP(OEt)2}N (4), (SPPh2)(O2SMe)N (5) and {SP(OEt)2}(O2SC6H4Cl-4)N (6)] were prepared by salt metathesis reactions between [{2-(Me2NCH2)C6H4}3Te]Cl•H2O and the potassium salts of the corresponding organophosphorus ligands in a 1:1 molar ratio. Multinuclear NMR spectroscopy, mass spectrometry, molar conductivity and IR spectroscopy were used to characterize the new complexes. The 1H NMR spectra suggest for all compounds the intramolecular coordination of the nitrogen atoms from the pendant arms to tellurium in solution. For compound 3 single-crystal X-ray diffraction studies revealed strong N→Te intramolecular interactions in solid state, which result in hypercoordinated triaryltelluronium(IV) cations (14‒Te‒6 species) with a distorted octahedral coordination geometry around tellurium. Weak S⋅⋅⋅H interactions between anions and cations resulted in a 2D supramolecular network.

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Section: Introduction *mentioning

confidence: 99%

New hypercoordinated triaryltelluronium derivatives of oraganophosphorus ligands. Synthesis and structural characterization

Denes¹,

Vlassa²,

Silvestru³

et al. 2021

Rev.Roum.Chim.

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Hypercoordinated triorganotellurium(IV) derivatives of chalcogen-centred organophosphorus ligands

Denes

Beleaga

Silvestru

2020

Inorganica Chimica Acta

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Synthesis and Characterization of Monomeric Hexacoordinated Chalcogenonium Salts Bearing 2-(2-Pyridyl)phenyl Ligands

Sato

Ooizumi

Sakabe

et al. 2021

Bulletin of the Chemical Society of Japan

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Consecutive treatment of 2-(2-lithiophenyl)pyridine with chalcogen tetrachlorides (ChCl4; Ch = Se and Te) and KPF6 afforded the hexafluorophosphate salts of tris[2-(2-pyridyl)phenyl]selenonium [(ppy)3Se]+ ([1]+) and tris[2-(2-pyridyl)phenyl]telluronium [(ppy)3Te]+ ([2]+), respectively. The chalcogenonium salts [1][PF6] and [2][PF6] exhibit extremely high thermal stability and high melting points. Their solid-state structures revealed distorted octahedral bonding geometries with a C3-symmetrical facial configuration. Quantum chemical calculations on [1]+ and [2]+ strongly suggest that their HOMO−3s involve lone pairs of electrons (LPs) on the central chalcogen atoms, and that the three Ch–N (Ch = Se and Te) bonds are formed by LP(N)→σ*(Ch–C) donor-acceptor interactions. Based on theoretical calculations and 77Se and 125Te NMR spectral data, the C–Ch–N moieties of [1]+ and [2]+ were characterized as asymmetrical three-center four-electron σ-type bonds [σ(3c–4e)]. Both organochalcogenonium salts represent novel monomeric hexacoordinated species that bear 14 formal valence electrons (14–Se–6 and 14–Te–6, respectively). A quantum theory of atoms-in-molecules dual functional analysis predicted that the C–Ch interaction of the σ(3c–4e) C–Ch–N moiety (Ch = Se and Te) is weakly covalent, while the Se–N and Te–N interactions were predicted to have the typical characteristics of hydrogen bonds and molecular complexes, respectively. The differences between [2][PF6] and the recently reported [2][Br] were also carefully examined.

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Experimental evidence for hypercoordination in triorganotelluronium halides with 2-(Me₂NCH₂)C₆H₄ groups

Abstract: Triorganotelluronium halides of type [{2-(Me2NCH2)C6H4}nPh3−nTe]+X− (n = 1–3, X = Cl, Br, I) were prepared and structurally characterized both in solution and in the solid state, showing a (C,N)-chelating behavior of the 2-(Me2NCH2)C6H4 groups.

Cited by 3 publications

References 43 publications

New hypercoordinated triaryltelluronium derivatives of oraganophosphorus ligands. Synthesis and structural characterization

New hypercoordinated triaryltelluronium derivatives of oraganophosphorus ligands. Synthesis and structural characterization

Hypercoordinated triorganotellurium(IV) derivatives of chalcogen-centred organophosphorus ligands

Synthesis and Characterization of Monomeric Hexacoordinated Chalcogenonium Salts Bearing 2-(2-Pyridyl)phenyl Ligands

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