Fluorinated elements of Group 15 as pnictogen bond donor sites

Scilabra, Patrick; Terraneo, Giancarlo; Resnati, Giuseppe

doi:10.1016/j.jfluchem.2017.10.002

Cited by 76 publications

(78 citation statements)

References 197 publications

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“…Intra-and intermolecular TBs are observed, and they can affect the preferred conformation of a molecule and/or the network of intermolecular interactions in the crystal packing. Importantly, the cases collected here provide convincing experimental evidence that TBs tend to be more linear than PBs [31].…”

Section: Introductionsupporting

confidence: 60%

“…Finally, the Sn···I interactions present in crystals of tris(trimethylstannyl)ammonium iodide (refcode RONDAZ) [125] provide a nice example of chargeassisted TB. The existence of this type of TB further highlights the similarities of the different subsets of σ-hole interactions, as charge-assisted XBs [126] and charge-assisted PBs [31] have already been observed. Specifically, two crystallographically independent salt units are present in the crystal of R O N D A Z ; i n b o t h o f t h e s e u n i t s , t h e tris(trimethylstannyl)ammonium cations act as tridentate TB donors and the iodide anion as a tridentate TB acceptor, and 3D networks are formed (one 3D network is shown in Fig.…”

Section: Halogen Atoms As Tetrel Bond Acceptorssupporting

confidence: 54%

“…The examined dataset is too limited to be able to draw general conclusions, but it seems to suggest that the deviation of a tetrel bond from the extension of the relevant covalent bond to a germanium or tin atom is usually smaller than the corresponding deviations for most PBs and CBs [31]. This is consistent with theoretical calculations which show that the region of most positive electrostatic potential opposite to a covalent bond deviates from the extension of the bond to the greatest extent in pnictogen derivatives and to the least extent in tetrel derivatives [134,135].…”

Section: Discussionmentioning

confidence: 97%

“…Chalcogen bonds (CBs) have been studied in silico [25,26] and in the solid [27], liquid [28], and gas [29] phases. Pnictogen bonds (PBs) have received much attention in studies performed in silico [30] and in the solid [31]; and the aerogen bond (AB) is the most recently discovered subset of σ-hole interactions [32].…”

Section: Introductionmentioning

confidence: 99%

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Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

et al. 2018

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Modeling indicates the presence of a region of low electronic density (a Bσ-hole^) on group 14 elements, and this offers an explanation for the ability of these elements to act as electrophilic sites and to form attractive interactions with nucleophiles. While many papers have described theoretical investigations of interactions involving carbon and silicon, such investigations of the heavier group 14 elements are relatively scarce. The purpose of this review is to rectify, to some extent, the current lack of experimental data on interactions formed by germanium and tin with nucleophiles. A survey of crystal structures in the Cambridge Structural Database is reported. This survey reveals that close contacts between Ge or Sn and lone-pair-possessing atoms are quite common, they can be either intra-or intermolecular contacts, and they are usually oriented along the extension of the covalent bond formed by the tetrel with the most electron-withdrawing substituent. Several examples are discussed in which germanium and tin atoms bear four carbon residues or in which halogen, oxygen, sulfur, or nitrogen substituents replace one, two, or three of those carbon residues. These close contacts are assumed to be the result of attractive interactions between the involved atoms and afford experimental evidence of the ability of germanium and tin to act as electrophilic sites, namely tetrel bond (TB) donors. This ability can govern the conformations and the packing of organic derivatives in the solid state. TBs can therefore be considered a promising and robust tool for crystal engineering.

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Section: Introductionsupporting

confidence: 60%

Section: Halogen Atoms As Tetrel Bond Acceptorssupporting

confidence: 54%

Section: Discussionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

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Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

et al. 2018

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“…[46] The increasedv alues for the EP minimao ft he terminal Fa toms on Ng in NgF 2 ·CrOF 4 (F Xe , À55;F Kr , À39 kJ mol À1 )r elative to those of free NgF 2 are consistentw ith polarization of the adducted NgF 2 moleculeb yc hromium. The fluorine ligands of NgF 2 in NgF 2 ·CrOF 4 andN gF 2 ·2CrOF 4 coordinate into these regions of high charge depletion.…”

Section: Molecularelectrostatic Potential Surface(meps)a Nalysesmentioning

confidence: 76%

Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

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Breddemann

Brock

et al. 2019

Chemistry A European J

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The noble‐gas difluoride adducts, NgF2⋅CrOF4 and NgF2⋅2CrOF4 (Ng=Kr and Xe), have been synthesized and structurally characterized at low temperatures by Raman spectroscopy and single‐crystal X‐ray diffraction. The low fluoride ion affinity of CrOF4 renders it incapable of inducing fluoride ion transfer from NgF2 (Ng=Kr and Xe) to form ion‐paired salts of the [NgF]+ cations having either the [CrOF5]− or [Cr2O2F9]− anions. The crystal structures show the NgF2⋅CrOF4 adducts are comprised of Ft−Ng−Fb‐ ‐ ‐Cr(O)F4 structural units in which NgF2 is weakly coordinated to CrOF4 by means of a fluorine bridge, Fb, in which Ng−Fb is elongated relative to the terminal Ng−Ft bond. In contrast with XeF2⋅2MOF4 (M=Mo or W) and KrF2⋅2MoOF4, in which the Lewis acidic, F4(O)M‐ ‐ ‐Fb‐ ‐ ‐M(O)F3 moiety coordinates to Ng through a single M‐ ‐ ‐Fb−Ng bridge, both fluorine ligands of NgF2 coordinate to CrOF4 molecules to form F4(O)Cr‐ ‐ ‐Fb−Ng−Fb‐ ‐ ‐Cr(O)F4 adducts in which both Ng−Fb bonds are only marginally elongated relative to the Ng−F bonds of free NgF2. Quantum‐chemical calculations show that the Cr−Fb bonds of NgF2⋅CrOF4 and NgF2⋅2CrOF4 are predominantly electrostatic with a small degree of covalent character that accounts for their nonlinear Cr‐ ‐ ‐Fb−Ng bridge angles and staggered O−Cr‐ ‐ ‐Fb−Ng−Ft dihedral angles. The crystal structures and Raman spectra of two CrOF4 polymorphs have also been obtained. Both are comprised of fluorine‐bridged chains that are cis‐ and trans‐fluorine‐bridged with respect to oxygen.

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A Stable Crown Ether Complex with a Noble‐Gas Compound

2018

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Crown ethers have been known for over 50 years, but no example of a complex between a noble‐gas compound and a crown ether or another polydentate ligand had previously been reported. Xenon trioxide is shown to react with 15‐crown‐5 to form the kinetically stable (CH2CH2O)5XeO3 adduct, which, in marked contrast with solid XeO3, does not detonate when mechanically shocked. The crystal structure shows that the five oxygen atoms of the crown ether are coordinated to the xenon atom of XeO3. The gas‐phase Wiberg bond valences and indices and the empirical bond valences indicate that the Xe‐ ‐ ‐Ocrown bonds are predominantly electrostatic and are consistent with σ‐hole bonding. Mappings of the electrostatic potential (EP) onto the Hirshfeld surfaces of XeO3 and 15‐crown‐5 in (CH2CH2O)5XeO3 and a detailed examination of the molecular electrostatic potential surface (MEPS) of XeO3 and (CH2CH2O)5 reveal regions of negative EP on the oxygen atoms of (CH2CH2O)5 and regions of high positive EP on the xenon atom, which are also in accordance with σ‐hole interactions.

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Fluorinated elements of Group 15 as pnictogen bond donor sites

Cited by 76 publications

References 197 publications

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

A Stable Crown Ether Complex with a Noble‐Gas Compound

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Fluorinated elements of Group 15 as pnictogen bond donor sites

Cited by 76 publications

References 197 publications

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

Syntheses, Structures, and Bonding of NgF2⋅CrOF4, NgF2⋅2CrOF4(Ng=Kr, Xe), and (CrOF4)∞

A Stable Crown Ether Complex with a Noble‐Gas Compound

Contact Info

Product

Resources

About

Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞