C(sp3) atoms as tetrel bond donors: A crystallographic survey

Daolio, Andrea; Scilabra, Patrick; Terraneo, Giancarlo; Resnati, Giuseppe

doi:10.1016/j.ccr.2020.213265

Cited by 76 publications

(76 citation statements)

References 221 publications

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“…Atoms from elements of groups 13-18 covalently bound to electron-withdrawing groups (EWGs) possess a strong ability to interact with Lewis bases (e.g., lone pair donors, anions, and π systems) [1][2][3][4][5][6][7][8][9][10][11][12][13]. Since the electropositive site was used to define the hydrogen bonding (HB) interaction, scientists have started to use the name of the group to which the electrophilic atom belongs to name the noncovalent interactions (NCIs) between electrophilic and nucleophilic sites [14,15].…”

Section: Introductionmentioning

confidence: 99%

On the Importance of σ–Hole Interactions in Crystal Structures

Frontera

Bauzá

2021

Crystals

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Elements from groups 14–18 and periods 3–6 commonly behave as Lewis acids, which are involved in directional noncovalent interactions (NCI) with electron-rich species (lone pair donors), π systems (aromatic rings, triple and double bonds) as well as nonnucleophilic anions (BF4−, PF6−, ClO4−, etc.). Moreover, elements of groups 15 to 17 are also able to act as Lewis bases (from one to three available lone pairs, respectively), thus presenting a dual character. These emerging NCIs where the main group element behaves as Lewis base, belong to the σ–hole family of interactions. Particularly (i) tetrel bonding for elements belonging to group 14, (ii) pnictogen bonding for group 15, (iii) chalcogen bonding for group 16, (iv) halogen bonding for group 17, and (v) noble gas bondings for group 18. In general, σ–hole interactions exhibit different features when moving along the same group (offering larger and more positive σ–holes) or the same row (presenting a different number of available σ–holes and directionality) of the periodic table. This is illustrated in this review by using several examples retrieved from the Cambridge Structural Database (CSD), especially focused on σ–hole interactions, complemented with molecular electrostatic potential surfaces of model systems.

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Section: Introductionmentioning

confidence: 99%

On the Importance of σ–Hole Interactions in Crystal Structures

Frontera

Bauzá

2021

Crystals

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“…On the other hand, sp 3 carbon atoms are generally found acting as Lewis acids in tetrel bonding 15 – 21 . More rarely, sp 3 carbon atoms have been described as electron density donors 22 .…”

Section: Introductionmentioning

confidence: 99%

Methyl groups as widespread Lewis bases in noncovalent interactions

Loveday

Echeverría

2021

Nat Commun

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It is well known that, under certain conditions, C(sp3) atoms behave, via their σ-hole, as Lewis acids in tetrel bonding. Here, we show that methyl groups, when bound to atoms less electronegative than carbon, can counterintuitively participate in noncovalent interactions as electron density donors. Thousands of experimental structures are found in which methyl groups behave as Lewis bases to establish alkaline, alkaline earth, triel, tetrel, pnictogen, chalcogen and halogen bonds. Theoretical calculations confirm the high directionality and significant strength of the interactions that arise from a common pattern based on the electron density holes model. Moreover, despite the absence of lone pairs, methyl groups are able to transfer charge from σ bonding orbitals into empty orbitals of the electrophile to reinforce the attractive interaction.

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“…While the geometry around osmium remains essentially tetrahedral (e.g., O‐Os‐O angles in 2 a span the range 101.5–117.7°), it becomes somewhat similar to a trigonal bipyramid, the incoming N or O atom occupying an apical position. A similar deformation from tetrahedral towards trigonal bipyramidal geometry is observed on formation of σ‐hole interactions involving tetravalent elements of group 14 [4, 34] . An elongation of the covalent bond opposite to the incoming nucleophile is common for σ‐hole interactions, [3, 4] and is usually rationalized as a consequence of the LP→σ* charge transfer.…”

Section: Figurementioning

confidence: 70%

“…A systematic rationalization of intermolecular interactions based on this mindset began in the 1990s when a region of most positive electrostatic potential, [1] the so called σ‐hole, [2] was found on the surface of halogen atoms in dihalogens and halocarbons and when soon after the resulting electrophilic character of halogens began to be exploited in supramolecular chemistry [3] . Analogous σ‐holes with positive electrostatic potential were successively identified on other elements of p‐block of the periodic table, for example, on elements of groups 14, [4] 15, [5] and 16 [6] . The attractive interactions occurring between these positive holes and nucleophilic sites are now topics of intense research in fields as diverse as drug design, [7] catalysis, [8] and anion transport [9] …”

Section: Figurementioning

confidence: 99%

Molecular Electrostatic Potential and Noncovalent Interactions in Derivatives of Group 8 Elements

et al. 2021

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This communication reports experimental and theoretical evidences of σ‐hole interactions in adducts between nitrogen or oxygen nucleophiles and tetroxides of osmium or other group 8 elements. Cocrystals between pyridine or pyridine N‐oxide derivatives and osmium tetroxide are characterized through various techniques and rationalized as σ‐hole interactions using DFT calculations and several other computational tools. We propose the term “osme bond” (OmB, Om=Fe, Ru, Os, (Hs)) for naming the noncovalent interactions wherein group 8 elements have the role of the electrophile. The word osme is the transcription of ὀσμή, the ancient Greek word for smell that was used to name the heaviest group 8 element in relation to the smoky odor of its tetroxide.

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C(sp3) atoms as tetrel bond donors: A crystallographic survey

Cited by 76 publications

References 221 publications

On the Importance of σ–Hole Interactions in Crystal Structures

On the Importance of σ–Hole Interactions in Crystal Structures

Methyl groups as widespread Lewis bases in noncovalent interactions

Molecular Electrostatic Potential and Noncovalent Interactions in Derivatives of Group 8 Elements

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