Weak yet Decisive: Molecular Halogen Bond and Competing Weak Interactions of Iodobenzene and Quinuclidine

Otte, Felix; Kleinheider, Johannes; Hiller, Wolf; Wang, Ruimin; Englert, Ulli; Strohmann, Carsten

doi:10.1021/jacs.1c00239

Cited by 30 publications

(49 citation statements)

References 56 publications

(55 reference statements)

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“…The question arises as to whether these same principles are in operation when the reaction in question is the formation of a halogen bond. There have been a number of works in the recent literature [31][32][33][34][35][36][37][38] that have studied the XB formed by a halogen-substituted phenyl ring, which have added to our body of knowledge but there are several important questions remaining.…”

Section: Introductionmentioning

confidence: 99%

Influence of Substituents in the Benzene Ring on the Halogen Bond of Iodobenzene with Ammonia

Scheiner

Hunter

2022

ChemPhysChem

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The effects on the CÀ I••N halogen bond between iodobenzene and NH 3 of placing various substituents on the phenyl ring are monitored by quantum calculations. Substituents R = N(CH 3 ) 2 , NH 2 , CH 3 , OCH 3 , COCH 3 , Cl, F, COH, CN, and NO 2 were each placed ortho, meta, and para to the I. The depth of the σ-hole on I is deepened as R becomes more electron-withdrawing which is reflected in a strengthening of the halogen bond, which varied between 3.3 and 5.5 kcal mol À 1 . In most cases, the ortho placement yields the largest perturbation, followed by meta and then para, but this trend is not universal. Parallel to these substituent effects is a progressive lengthening of the covalent CÀ I bond. Formation of the halogen bond reduces the NMR chemical shielding of all three nuclei directly involved in the CÀ I••N interaction. The deshielding of the electron donor N is most closely correlated with the strength of the bond, as is the coupling constant between I and N, so both have potential use as spectroscopic measures of halogen bond strength.

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Section: Introductionmentioning

confidence: 99%

Influence of Substituents in the Benzene Ring on the Halogen Bond of Iodobenzene with Ammonia

Scheiner

Hunter

2022

ChemPhysChem

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“…More recently, halogen bonds and related interactions have gained increasing attention from theory [ 11 , 12 , 13 , 14 ], and the

-hole model has also been supported by experimental charge density studies [ 15 , 16 , 17 , 18 , 19 ]. In view of their occurrence in various fields, including macromolecular and supramolecular chemistry, halogen bonds have also been applied in the design of extended solids, i.e., in crystal engineering [ 20 ].…”

Section: Introductionmentioning

confidence: 99%

Hydrogen-Bonded and Halogen-Bonded: Orthogonal Interactions for the Chloride Anion of a Pyrazolium Salt

et al. 2021

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In the hydrochloride of a pyrazolyl-substituted acetylacetone, the chloride anion is hydrogen-bonded to the protonated pyrazolyl moiety. Equimolar co-crystallization with tetrafluorodiiodobenzene (TFDIB) leads to a supramolecular aggregate in which TFDIB is situated on a crystallographic center of inversion. The iodine atom in the asymmetric unit acts as halogen bond donor, and the chloride acceptor approaches the σ-hole of this TFDIB iodine subtending an almost linear halogen bond, with Cl···I = 3.1653(11) Å and Cl···I–C = 179.32(6)°. This contact is roughly orthogonal to the N–H···Cl hydrogen bond. An analysis of the electron density according to Bader’s Quantum Theory of Atoms in Molecules confirms bond critical points (bcps) for both short contacts, with ρbcp = 0.129 for the halogen and 0.321eÅ−3 for the hydrogen bond. Our halogen-bonded adduct represents the prototype for a future class of co-crystals with tunable electron density distribution about the σ-hole contact.

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“…Among this framework, halobenzenes are an interesting class of halogen-bond donors, R–X, because halogen atoms X can be easily introduced into a benzene ring at different positions. In addition, these compounds provide a convenient platform for introducing substituents and investigating, experimentally and theoretically, their effects on the ability of X to mediate halogen-bond interactions (i.e., halogen-bond tuning) [ 11 , 12 , 13 , 14 , 15 , 16 , 17 ]. Currently, it is commonly recognized that the interaction strength increases as R is more electron-withdrawing, and for a given R, in the order X = F < Cl < Br < I, following the trend in the halogens’ polarizabilities (and decreasing electronegativities) [ 2 , 10 , 18 ].…”

Section: Introductionmentioning

confidence: 99%

Astatine Facing Janus: Halogen Bonding vs. Charge-Shift Bonding

et al. 2021

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The nature of halogen-bond interactions was scrutinized from the perspective of astatine, potentially the strongest halogen-bond donor atom. In addition to its remarkable electronic properties (e.g., its higher aromaticity compared to benzene), C6At6 can be involved as a halogen-bond donor and acceptor. Two-component relativistic calculations and quantum chemical topology analyses were performed on C6At6 and its complexes as well as on their iodinated analogues for comparative purposes. The relativistic spin–orbit interaction was used as a tool to disclose the bonding patterns and the mechanisms that contribute to halogen-bond interactions. Despite the stronger polarizability of astatine, halogen bonds formed by C6At6 can be comparable or weaker than those of C6I6. This unexpected finding comes from the charge-shift bonding character of the C–At bonds. Because charge-shift bonding is connected to the Pauli repulsion between the bonding σ electrons and the σ lone-pair of astatine, it weakens the astatine electrophilicity at its σ-hole (reducing the charge transfer contribution to halogen bonding). These two antinomic characters, charge-shift bonding and halogen bonding, can result in weaker At-mediated interactions than their iodinated counterparts.

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Weak yet Decisive: Molecular Halogen Bond and Competing Weak Interactions of Iodobenzene and Quinuclidine

Cited by 30 publications

References 56 publications

Influence of Substituents in the Benzene Ring on the Halogen Bond of Iodobenzene with Ammonia

Influence of Substituents in the Benzene Ring on the Halogen Bond of Iodobenzene with Ammonia

Hydrogen-Bonded and Halogen-Bonded: Orthogonal Interactions for the Chloride Anion of a Pyrazolium Salt

Astatine Facing Janus: Halogen Bonding vs. Charge-Shift Bonding

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