Computational evidence that hyperconjugative orbital interactions are responsible for the stability of intramolecular Te⋯O/Te⋯S non-covalent interactions and comparable to hydrogen bonds in quasi-cyclic systems

Si, Mrinal Kanti

doi:10.1039/c6nj01707j

Cited by 10 publications

(4 citation statements)

References 56 publications

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“…Theoretical investigations on ChBs are mostly based on quantum mechanical calculations utilizing second order Mø ller-Plesset perturbation theory − or density functional theory (DFT), ,,− where the accuracy of these methods are often validated by high accuracy CCSD(T) single point energy calculations of a subset of complexes. ,− ,− These investigations were carried to better understand: (i) the ChB bonding mechanism, (ii) the dominant forces involved in the formation of the ChB, (iii) the high directionality of the ChBs, ,− (iv) the strength of the ChB and how it can be fine-tuned (v) to compare ChB with other SBIs (vi) and to support experimental analyses.…”

Section: Introductionmentioning

confidence: 99%

The Many Facets of Chalcogen Bonding: Described by Vibrational Spectroscopy

2017

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A diverse set of 100 chalcogen-bonded complexes comprising neutral, cationic, anionic, divalent, and double bonded chalcogens has been investigated using ωB97X-D/aug-cc-pVTZ to determine geometries, binding energies, electron and energy density distributions, difference density distributions, vibrational frequencies, local stretching force constants, and associated bond strength orders. The accuracy of ωB97X-D was accessed by CCSD(T)/aug-cc-pVTZ calculations of a subset of 12 complexes and by the CCSD(T)/aug-cc-pVTZ //ωB97X-D binding energies of 95 complexes. Most of the weak chalcogen bonds can be rationalized on the basis of electrostatic contributions, but as the bond becomes stronger, covalent contributions can assume a primary role in the strength and geometry of the complexes. Covalency in chalcogen bonds involves the charge transfer from a lone pair orbital of a Lewis base into the σ* orbital of a divalent chalcogen or a π* orbital of a double bonded chalcogen. We describe for the first time a symmetric chalcogen-bonded homodimer stabilized by a charge transfer from a lone pair orbital into a π* orbital. New polymeric materials based on chalcogen bonds should take advantage of the extra stabilization granted by multiple chalcogen bonds, as is shown for 1,2,5-telluradiazole dimers.

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Section: Introductionmentioning

confidence: 99%

The Many Facets of Chalcogen Bonding: Described by Vibrational Spectroscopy

2017

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“…The phenomenon of CB currently attracts great attention due to applicability of CB in biochemistry, drug design, , polymer science, crystal engineering, and supramolecular chemistry . Although heavier chalcogens, Se and Te, , are better CB donors because of their higher polarizability, − the majority of recent reports deal with CBs involving more abundant S centers. Most common types of CB with S atoms are S···S, S···O, and S···N interactions that are widely available in proteins − and also in some organic compounds. ,,, The CBs of sulfur with halogens (particularly with Cl centers in both organic species and metal complexes) are also known, albeit still unusual.…”

Section: Introductionmentioning

confidence: 99%

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd^II Complexes

et al. 2016

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The reaction of cis-[PdCl(CNXyl)] (Xyl = 2,6-MeCH) with various 1,3-thiazol- and 1,3,4-thiadiazol-2-amines in chloroform gives a mixture of two regioisomeric binuclear diaminocarbene complexes. For 1,3-thiazol-2-amines the isomeric ratio depends on the reaction conditions and kinetically (KRs) or thermodynamically (TRs) controlled regioisomers were obtained at room temperature and on heating, respectively. In CHCl solutions, the isomers are subject to reversible isomerization accompanied with the cleavage of Pd-N and С-N bonds in the carbene fragment XylNCN(R)Xyl. Results of DFT calculations followed by the topological analysis of the electron density distribution within the formalism of Bader's theory (AIM method) reveal that in CHCl solution the relative stability of the regioisomers (∆G = 1.2 kcal/mol; ∆G = 3.2 kcal/mol) is determined by the energy difference between two types of the intramolecular chalcogen bonds, viz. S•••Cl in KRs (2.8-3.0 kcal/mol) and S•••N in TRs (4.6-5.3 kcal/mol). In the case of the 1,3,4-thiadiazol-2-amines, the regioisomers are formed in approximately equal amounts and, accordingly, the energy difference between these species is only 0.1 kcal/mol in terms of ∆G (∆G = 2.1 kcal/mol). The regioisomers were characterized by elemental analyses (C, H, N), HRESI-MS and FTIR, 1D (H, C) and 2D (H,H-COSY, H,H-NOESY, H,C-HSQC, H,C-HMBC) NMR spectroscopies, and structures of six complexes (three KRs and three TRs) were elucidated by single-crystal X-ray diffraction.

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“…The other reason is, that SBIs have more covalent character, but lighter chalcogens like oxygen or sulfur tend to interact with σ‐holes, whereas heavier chalcogen atoms like tellurium are more prone to hyperconjugation. For σ‐hole interactions like S⋅⋅⋅O and S⋅⋅⋅S, the electrostatic effect is decreasing due to less electronegativity of the outer atom, while the hyperconjugation for Te⋅⋅⋅O and Te⋅⋅⋅S increases due to better overlap [47] . If the chalcogen has more substituents, more σ‐holes are generated [48] …”

Section: Resultsmentioning

confidence: 99%

New Crystal Structures of Rare‐Earth Metal(III) Oxotellurates(IV) RE₂Te₃O₉: A1‐Type (RE=La, Ce) and A2‐Type (RE=Pr, Nd)

Chou

Höss

Russ

et al. 2021

Zeitschrift anorg allge chemie

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The new rare‐earth metal(III) oxotellurates(IV) RE2Te3O9 (RE=La−Nd) of the so far unknown A‐type structure can be obtained as needle‐shaped single crystals through solid‐state reactions of the corresponding binary oxides. Their crystal structures were determined as A1‐type for RE=La and Ce or A2‐type for RE=Pr and Nd by single‐crystal X‐ray diffraction. Both structure types crystallize in the monoclinic crystal system, but in two different non‐centrosymmetric space groups: the A1‐type with Z=8 in space group P21 (La2Te3O9: a=569.54(3), b=2230.12(13), c=1464.71(4) pm, β=101.205(3)°; Ce2Te3O9: a=567.02(3), b=2222.61(13), c=1457.13(9) pm, β=101.134(3)°) or the A2‐type with Z=16 in space group Cc (Pr2Te3O9: a=2838.61(16), b=563.89(3), c=2522.08(15) pm, β=118.816(3)°; Nd2Te3O9: a=2826.38(16), b=561.47(3), c=2511.94(15) pm, β=118.841(3)°). In spite of the differences in the unit‐cell parameters and the symmetry, both structures consist of quite similar fundamental building blocks (FBBs) consisting of eight crystallographically distinct rare‐earth metal‐oxygen polyhedra with C.N.(RE3+) from seven to nine and always twelve different ψ1‐tetrahedral oxotellurate(IV) anions [TeO3]2−, which show a high number of secondary bonding interactions (SBIs) with each other in all four cases.

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Computational evidence that hyperconjugative orbital interactions are responsible for the stability of intramolecular Te⋯O/Te⋯S non-covalent interactions and comparable to hydrogen bonds in quasi-cyclic systems

Abstract: The intramolecular secondary bonding interactions involving quasi-cyclic tellurium are comparable to H-bond strength and partially governed by orbital interactions.

Cited by 10 publications

References 56 publications

The Many Facets of Chalcogen Bonding: Described by Vibrational Spectroscopy

The Many Facets of Chalcogen Bonding: Described by Vibrational Spectroscopy

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd^II Complexes

New Crystal Structures of Rare‐Earth Metal(III) Oxotellurates(IV) RE₂Te₃O₉: A1‐Type (RE=La, Ce) and A2‐Type (RE=Pr, Nd)

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Computational evidence that hyperconjugative orbital interactions are responsible for the stability of intramolecular Te⋯O/Te⋯S non-covalent interactions and comparable to hydrogen bonds in quasi-cyclic systems

Abstract: The intramolecular secondary bonding interactions involving quasi-cyclic tellurium are comparable to H-bond strength and partially governed by orbital interactions.

Cited by 10 publications

References 56 publications

The Many Facets of Chalcogen Bonding: Described by Vibrational Spectroscopy

The Many Facets of Chalcogen Bonding: Described by Vibrational Spectroscopy

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)PdII Complexes

New Crystal Structures of Rare‐Earth Metal(III) Oxotellurates(IV) RE2Te3O9: A1‐Type (RE=La, Ce) and A2‐Type (RE=Pr, Nd)

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Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd^II Complexes

New Crystal Structures of Rare‐Earth Metal(III) Oxotellurates(IV) RE₂Te₃O₉: A1‐Type (RE=La, Ce) and A2‐Type (RE=Pr, Nd)