Geminal Charge-Assisted Tetrel Bonds in Bis-Pyridinium Methylene Salts

Calabrese, Miriam; Pizzi, Andrea; Daolio, Andrea; Ursini, Maurizio; Frontera, Antonio; Demitri, Nicola; Lenczyk, Carsten; Wojciechowski, Jakub; Resnati, Giuseppe

doi:10.1021/acs.cgd.2c01386

Cited by 4 publications

(2 citation statements)

References 31 publications

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“…In addition to adding to our currently sparse knowledge about pentacoordinate C, the results will also inform our building knowledge base about noncovalent tetrel bonding. [9][10][11][12][13][14][15][16][17][18]…”

Section: Introductionmentioning

confidence: 99%

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Tetrel Bonding of the Carbenium Ion Forms a Pentacoordinate Carbon Atom

Scheiner

2024

ChemPhysChem

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As a flat trigonal species, the CR3+ carbenium ion contains a pair of deep π‐holes above and below its molecular plane. In the case of CH3+ a first base will form a covalent bond with the central C, making the combined species tetrahedral. Approach of a second base to the opposite side results in a longer but rather strong noncovalent tetrel bond (TB). While the CMe3+ can also form a similar asymmetric complex with a pair of bases, it also has the capacity to form a pair of nearly equivalent TBs, such that the resulting symmetric trigonal bipyramid configuration is only slightly higher in energy. When the three substituents on the central C are phenyl rings, the symmetric configuration with two TBs predominates. These tetrel bonds are quite strong, reaching up to 20 kcal/mol. Adding OPH2 or OCH substituents to the phenyl rings permits the formation of intramolecular C··O TBs to the central C, very similar in many respects to the case where these TBs are intermolecular.

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Section: Introductionmentioning

confidence: 99%

“…The results permit an elucidation of how certain intramolecular constraints might affect the conclusions arrived at by studying intermolecular contacts. In addition to adding to our currently sparse knowledge about pentacoordinate C, the results will also inform our building knowledge base about noncovalent tetrel bonding [9–18] …”

Section: Introductionmentioning

confidence: 99%

Tetrel Bonding of the Carbenium Ion Forms a Pentacoordinate Carbon Atom

Scheiner

2024

ChemPhysChem

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Osme Bond: Geometric and Energetic Features in the Adducts between OsO₄ and Lewis Bases

Calabrese,

Pizzi,

Daolio

et al. 2024

Chemistry A European J

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Adducts between OsO4 and Lewis bases exert a role in important oxidation processes such as epoxidation and dihydroxylation. It has been shown that the attractive interaction driving the formation of these adducts is a σ‐hole bond involving the metal as the electrophilic species; the term Osme Bond (OmB) was proposed for designating it. Here some new adducts between OsO4 and various bases have been characterized through single crystal x‐ray diffraction (XRD) and computational studies (density functional theory, DFT), confirming the existence of a robust correlation between σ‐hole interaction energy and deformation of the tetrahedral geometry of OsO4. Also some adducts formed by RuO4 with nucleophiles were investigated computationally.

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Selective Activation of Chalcogen Bonding: An Efficient Structuring Tool toward Crystal Engineering Strategies

Dhaka,

Jeon,

Fourmigué

2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations * sı Supporting Information CONSPECTUS: Among the noncovalent interactions available in the toolbox of crystal engineering, chalcogen bonding (ChB) has recently entered the growing family of σ-hole interactions, following the strong developments based on the halogen bonding (XB) interaction over the last 30 years. The monovalent character of halogens provides halogen bonding directionality and strength. Combined with the extensive organic chemistry of Br and I derivatives, it has led to many applications of XB, in solution (organocatalysis, anion recognition and transport), in the solid state (cocrystals, conducting materials, fluorescent materials, topochemical reactions, ...), in soft matter (liquid crystals, gels,•••), and in biochemistry. The recognition of the presence of two σ-holes on divalent chalcogens and the ability to activate them, as in XB, with electron-withdrawing groups (EWG) has fueled more recent interest in chalcogen bonding. However, despite being identified for many years, ChB still struggles to make a mark due to (i) the underdeveloped synthetic chemistry of heavier Se and Te; (ii) the limited stability of organic chalcogenides, especially tellurides; and (iii) the poor predictability of ChB associated with the presence of two σ-holes. It therefore invites a great deal of attention of molecular chemists to design and develop selected ChB donors, for the scrutiny of fundamentals of ChB and their successful use in different applications. This Account aims to summarize our own contributions in this direction that extend from fundamental studies focused on addressing the lack of directionality/predictability in ChB to a systematic demonstration of its potential, specifically in crystal engineering, and particularly toward anionic networks on the one hand, topochemical reactions on the other hand.In this Account, we share our recent results aimed at recovering with ChB the same degree of strength and predictability found with XB, by focusing on divalent Se and Te systems with two different substituents, one of them with an EWG, to strongly unbalance both σ-holes. For that purpose, we explored this dissymmetrization concept within three chemical families, selenocyanates R−SeCN, alkynyl derivatives R−C�C−(Se/Te)Me, and o-carborane derivatives. Such compounds were systematically engaged in cocrystals with either halides or neutral bipyridines as ChB acceptors, revealing their strong potential to chelate halides as well as their ability to organize reactive molecules such as alkenes and butadiynes toward [2+2] cycloadditions and polydiacetylene formation, respectively. This selective activation concept is not limited to ChB but can be effectively used on all other σ-hole interactions (pnictogen bond, tetrel bond, etc.) where one needs to control the directionality of the interaction.■ KEY REFERENCES• Huynh, H.-T.; Jeannin, O.; Fourmigué, M. Organic selenocyanates as strong and directional chalcogen bond donors for crystal engineering. Chem. Commun. 2017, 53, 84...

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Geminal Charge-Assisted Tetrel Bonds in Bis-Pyridinium Methylene Salts

Cited by 4 publications

References 31 publications

Tetrel Bonding of the Carbenium Ion Forms a Pentacoordinate Carbon Atom

Tetrel Bonding of the Carbenium Ion Forms a Pentacoordinate Carbon Atom

Osme Bond: Geometric and Energetic Features in the Adducts between OsO₄ and Lewis Bases

Selective Activation of Chalcogen Bonding: An Efficient Structuring Tool toward Crystal Engineering Strategies

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Geminal Charge-Assisted Tetrel Bonds in Bis-Pyridinium Methylene Salts

Cited by 4 publications

References 31 publications

Tetrel Bonding of the Carbenium Ion Forms a Pentacoordinate Carbon Atom

Tetrel Bonding of the Carbenium Ion Forms a Pentacoordinate Carbon Atom

Osme Bond: Geometric and Energetic Features in the Adducts between OsO4 and Lewis Bases

Selective Activation of Chalcogen Bonding: An Efficient Structuring Tool toward Crystal Engineering Strategies

Contact Info

Product

Resources

About

Osme Bond: Geometric and Energetic Features in the Adducts between OsO₄ and Lewis Bases