Iodine–Iodine Bonding makes Tetra(diiodine)chloride, [Cl(I2)4]−, Planar

Walbaum, Christine; Richter, Mark M.; Sachs, Ulf; Pantenburg, Ingo; Riedel, Sebastian; Mudring, Anja‐Verena; Meyer, Gerd

doi:10.1002/anie.201305412

Cited by 35 publications

(34 citation statements)

References 19 publications

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“…For systems b–e , the sequence of the well depths (energy differences between local maxima and minima) is predicted correctly ( c < d < b < e ) at the M06‐2X‐D3/cc‐pVTZ level with references to the CCSD(T) results, although the absolute values are overestimated to some extent. At last, the optimal Cl···Cl distance in complex f is 12.2 Å (Supporting Information Table S1), or only 0.210 Å longer than the value obtained at the SCSMP2/def2‐TZVPP level of theory . In general, the M06‐2X‐D3/cc‐pVTZ level, adopted in the present study, provides us reliable results for both H‐ and X‐bonding systems with “AE” characteristic.…”

Section: Theoretical Backgroundsmentioning

confidence: 52%

“…In fact, some “anti‐electrostatic” X‐bonds (“AEXB”) were already observed experimentally. Walbaum et al showed that the tetra(diiodine)chloride ([Cl(I 2 ) 4 ] – ) dimer exhibits kinetic stability . Similarly, Martí‐Rujas et al made the tetrahalide anion [I 2 Cl 2 ] 2– , and found it to be a linear complex, Cl – ···I 2 ···Cl – , involving X‐bonds between a central I 2 molecule and two Cl – anions.…”

Section: Introductionmentioning

confidence: 99%

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Hydrogen‐ and Halogen‐Bonds between Ions of like Charges: Are They Anti‐Electrostatic in Nature?

Wang

Zhang

et al. 2017

J Comput Chem

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Recent theoretical studies suggested that hydrogen bonds between ions of like charges are of a covalent nature due to the dominating n →σ* charge-transfer (CT) interaction. In this work, energy profiles of typical hydrogen (H) and halogen (X) bonding systems formed from ions of like charges are explored using the block-localized wavefunction (BLW) method, which can derive optimal geometries and wave functions with the CT interaction "turned off." The results demonstrate that the kinetic stability, albeit reduced, is maintained for most investigated systems even after the intermolecular CT interaction is quenched. Further energy decomposition analyses based on the BLW method reveal that, despite a net repulsive Coulomb repulsion, a stabilizing component exists due to the polarization effect that plays significant role in the kinetic stability of all systems. Moreover, the fingerprints of the augmented electrostatic interaction due to polarization are apparent in the variation patterns of the electron density. All in all, much like in standard H- and X-bonds, the stability of such bonds between ions of like charges is governed by the competition between the stabilizing electrostatic and charge transfer interactions and the destabilizing deformation energy and Pauli exchange repulsion. While in most cases of "anti-electrostatic" bonds the CT interaction is of a secondary importance, we also find cases where CT is decisive. As such, this work validates the existence of anti-electrostatic H- and X-bonds. © 2017 Wiley Periodicals, Inc.

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Section: Theoretical Backgroundsmentioning

confidence: 52%

Section: Introductionmentioning

confidence: 99%

Hydrogen‐ and Halogen‐Bonds between Ions of like Charges: Are They Anti‐Electrostatic in Nature?

Wang

Zhang

et al. 2017

J Comput Chem

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“…In recent years, the spin‐component‐scaled second‐order Møller–Plesset (SCS‐MP2) theory, in which the opposite spin is enlarged and the same spin is scaled down in order to improve the description of molecular ground state energy, has been proved to be reliable for the study of non‐covalent interactions . Indeed, it has been widely adopted in the investigation of the newly discovered higher polychloride and polybromide monoanions . Note that, the structures of polyhalogen monoanions can be affected by the environment.…”

Section: Methodsmentioning

confidence: 99%

“…To date, polyiodides with different iodine contents from [I 3 ] − to [I 29 ] 3− have been reported, and a series of polybromides and polychlorides have also been experimentally identified . Moreover, two‐dimensional structures constructed by polychlorides or polyinterhalides have been experimentally observed. Compared with the richness of the widely explored polyiodides, the polyhalogens of lighter halogens are much less explored.…”

Section: Introductionmentioning

confidence: 99%

Halogen Bonds in Novel Polyhalogen Monoanions

Wang

Danovich

Shaik

et al. 2017

Chemistry A European J

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Polyhalogen monoanions [X ] (X=Cl and Br; n=1, 2, 3, 4, and 5) have been systematically studied using the block-localized wave function (BLW) method, which offers a valence bond (VB) analysis. For each species, the most stable isomer can be described as a central halide anion X non-classically bonded to a number of dihalogen molecules X via "halogen bonds". VB analyses confirm the dominant role of the charge-transfer interaction between the lone pair on X and the σ-anti-bonding orbital of X molecule (n→σ*) in X and higher analogues. Thus, our study demonstrates that these halogen bonds are essentially dative covalent interactions. Importantly, the charge-transfer interaction between [X ] and X decreases with the increasing n, in accord with the weakening of the Lewis basicity as characterized by the corresponding HOMO energy. The reduction of the charge transfer interaction underscores the reduction of covalence in halogen bonds in [X ] . This tendency highlights the anti-cooperative effect in polyhalogen monoanions. All in all, the halogen bond between X and nX molecules exhibits the same trends as in X with a single X molecule. In other words, halogen bonding in the larger clusters derives from the same bonding mechanism as the [X ] anion. As such, the X ⋅⋅⋅X halogen bond at different bond lengths forms a gauge of covalence for the entire [X ] family.

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“…Alternativ lässt sich die Verbindung aus Ytriumtriiodid, Natriumchlorid und Iod erhalten. Nach DFT‐Rechnungen ist das Nonahalogenidion aufgrund von Iod‐Iod‐π‐Bindungen planar 120. Die Umsetzung von Bis(triphenylphosphan)iminiumbromid (Ph3P)2 NBr mit einem Überschuss an elementarem Brom liefert das Undecabromid [(Ph3P)2N][Br11·Br2] (57) .…”

Section: Chalkogene Halogene Und Edelgaseunclassified

Anorganische Chemie 2013

Fischer

Welgand²

2014

Nachr Chem

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Hauptgruppenelemente: Carbene und ihre Homologen sowie die Suche nach dem Außergewöhnlichen — seien es bislang unbekannte Strukturmotive oder Bindungsverhältnisse. Koordinationschemie: Metall‐Metall‐Mehrfachbindungen zwischen zwei unterschiedlichen 3d‐Metallen; Funktion der Arrangements in der supramolekularen Chemie. Bioanorganik: Umsetzung der “kleinen Teilchen” H2, O2, N2 und e− und Einsatz anorganischer Verbindungen für die Pharmazie.

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Iodine–Iodine Bonding makes Tetra(diiodine)chloride, [Cl(I₂)₄]⁻, Planar

Cited by 35 publications

References 19 publications

Hydrogen‐ and Halogen‐Bonds between Ions of like Charges: Are They Anti‐Electrostatic in Nature?

Hydrogen‐ and Halogen‐Bonds between Ions of like Charges: Are They Anti‐Electrostatic in Nature?

Halogen Bonds in Novel Polyhalogen Monoanions

Anorganische Chemie 2013

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