Halogen Bonds of Iodonium Ions: A World Dissimilar to Silver Coordination

Turunen, Lotta; Németh, Flóra Boróka; Decato, Daniel A.; Pápai, Imre; Berryman, Orion B.; Erdélyi, Máté

doi:10.1246/bcsj.20200274

Cited by 7 publications

(7 citation statements)

References 32 publications

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“…Despite the similarities, XB is still not as well studied as HB is. Much of the recent XB research on the donor systems has concentrated on nonperfluorinated iodine based XB donors like iodonium (I + ), − I 2 , − and tetraiodoethylene. , On the XB acceptor side, a large part of the recent XB research has been focused on nitrogen compounds, although other XB applications, such as anion recognition, ,− have been actively researched and shown to be useful, e.g., as analytical tools. Out of the other possible XB acceptors, neutral sulfur species have attracted relatively little attention, but, for example, two studies on weak XBs of the title thiocarbonyl compounds were recently reported. , …”

Section: Introductionmentioning

confidence: 99%

Halogen Bonding between Thiocarbonyl Compounds and 1,2- and 1,4-Diiodotetrafluorobenzenes

Happonen

Rautiainen

Valkonen

2021

Crystal Growth & Design

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The halogen bonding (XB) between 1,2-diiodotetrafluorobenzene (1,2-DITFB) or 1,4-diiodotetrafluorobenzene (1,4-DITFB) and the selection of different thiocarbonyl acceptors was studied by the single-crystal X-ray diffraction method. Diiodotetrafluorobenzenes (DITFBs) were found to form C-I···S halogen-bonded 1:1, 2:1, and 1:2 (donor/acceptor ratio) complexes with thiocarbonyls. Lengths of contacts were found to be clearly shorter than the sum of van der Waals radii of iodine and sulfur as well as the contact angles showed values close to linear, so the XB interactions could be verified. One sulfur atom showed the ability to accept one, two, or four XB interactions, and the acceptor angle can vary more than 35°. Solid-state packing of thiocarbonyl-XB complexes was found to be greatly affected by the size and type of the acceptor used. Halogen and hydrogen bonding cooperativity was found in some of the complexes if the used acceptor was suitable to form both bonds. Here, we present 19 new structures of these complexes, which can be rather easily prepared by mixing the components in the solutions and letting them crystallize in loosely sealed tubes. Computational analysis carried out for the XB complexes of N,N′-dimethylthiourea supported very closely the findings of the experimental study.

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Section: Introductionmentioning

confidence: 99%

Halogen Bonding between Thiocarbonyl Compounds and 1,2- and 1,4-Diiodotetrafluorobenzenes

Happonen

Rautiainen

Valkonen

2021

Crystal Growth & Design

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“…13,19 These bonds have sometimes been referred to as "coordinative halogen bonds" or "halogen bonds with coordinative nature", 41,42 which are terms that are misleading and should be avoided. Halogen(I) complexes do not behave as coordinative transition metal complexes, 43 for example, when exposed to solvents and counterions. 44 The bond has occasionally also been named a halonium bond 45 and the complexes superhalides.…”

Section: ■ Terminologymentioning

confidence: 99%

Halogen Bonds of Halogen(I) Ions─Where Are We and Where to Go?

Wieske,

Erdelyi

2023

J. Am. Chem. Soc.

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Halenium ions, X + , are particularly strong halogen-bond donors that interact with two Lewis bases simultaneously to form linear [D•••X•••D] + -type halonium complexes. Their three-center, four-electron halogen bond is both fundamentally interesting and technologically valuable as it tames the reactivity of halogen(I) ions, opening up new horizons in a variety of fields including synthetic organic and supramolecular chemistry. Understanding this bonding situation enables the development of improved halogen(I) transfer reactions and of advanced functional materials. Following a decade of investigations of basic principles, the range of applications is now rapidly widening. In this Perspective, we assess the status of the field and identify its key advances and the main bottlenecks. Clearing common misunderstandings that may hinder future progress, we aim to inspire and direct future research efforts.

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“…[12,15,26,27] Good examples of highly polarized organic halogen bond donors are diiodotetrafluorobenzenes (DITFBs). [28][29][30][31] Rather recently found type of XB are three-center-four-electron bonds with highly polarized halogen (X) and two acceptor (A) atoms in [A [32][33][34][35] In this experimental study our aim was to synthesize tritopic thiourea based receptor molecules, which have three XB acceptor sites and to utilize them in further XB studies to understand better the behavior and capacities of sulfur in XB.…”

Section: Introductionmentioning

confidence: 99%

“…Good examples of highly polarized organic halogen bond donors are diiodotetrafluorobenzenes (DITFBs) [28–31] . Rather recently found type of XB are three‐center‐four‐electron bonds with highly polarized halogen (X) and two acceptor (A) atoms in [A 1 ⋅⋅⋅X⋅⋅⋅A 2 ] + system [32–35] …”

Section: Introductionmentioning

confidence: 99%

Thiourea‐Based Tritopic Halogen‐Bonding Acceptors

Happonen¹,

Mattila²,

Peshev³

et al. 2023

Chemistry An Asian Journal

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A series of thiourea‐based tritopic receptor molecules were synthesized to be used as building blocks for halogen‐bonded assemblies. Here, 16 new receptor molecules were synthesized from two different 2,4,6‐trialkyl‐1,3,5‐tris(bromomethyl)benzene starting materials via tris(isothiocyanatomethyl)benzene intermediates. The alkyl substituents in the benzene ring proved to be important for isothiocyanate group formation instead of competing thiocyanate group. The synthesis route allowed us to synthesize the isothiocyanate intermediates and further the receptor molecules without the typically used and highly toxic thiophosgene. The synthesized receptor molecules were used to study their halogen‐bond acceptor properties with diiodotetrafluorobenzene donors by single‐crystal X‐ray diffraction method. We were able to obtain five new crystal structures of halogen‐bonded complexes, in which all receptors showed two to four accepted C−I⋅⋅⋅S halogen bonds. The observed halogen bonds were highly directional and showed large variation in C=S⋅⋅⋅I acceptor angles, indicating flexible acceptor properties of sulfur.

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Halogen Bonds of Iodonium Ions: A World Dissimilar to Silver Coordination

Cited by 7 publications

References 32 publications

Halogen Bonding between Thiocarbonyl Compounds and 1,2- and 1,4-Diiodotetrafluorobenzenes

Halogen Bonding between Thiocarbonyl Compounds and 1,2- and 1,4-Diiodotetrafluorobenzenes

Halogen Bonds of Halogen(I) Ions─Where Are We and Where to Go?

Thiourea‐Based Tritopic Halogen‐Bonding Acceptors

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