On the non-existence of a square-planar pentaiodide coordination complex I(i)4− DOI Creative Commons
Lars Kloo

Dalton Transactions, Journal Year: 2022, Volume and Issue: 51(37), P. 14182 - 14189

Published: Jan. 1, 2022

The properties of two conformers the pentaiodide ion, a V-shaped and regularly observed I5- so far undetected square-planar coordination complex II4- composition, have been investigated by computational methods. latter compound is indicated analogy to chemistry gold with halide ligands, as well isoelectronic main-group compounds. Static dynamic simulations at density-functional semi-empirical level including effects solvent counter ions indicate that indeed represents well-defined local minimum on potential energy surface, albeit less stable than typically I5-. No simple pathway transformation between forms ion can be identified. Molecular dynamics presence cations, unavoidable during synthesis polyiodide compounds, may trigger decomposition into smaller building blocks thus constitute main reason why this conformer has not identified in solid However, its intrinsic stability indicates form should possible isolate compounds given right conditions synthesis.

Language: Английский

Halogen Bonds of Halogen(I) Ions─Where Are We and Where to Go? DOI Creative Commons
Lianne H. E. Wieske, Máté Erdélyi

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 3 - 18

Published: Dec. 20, 2023

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) opening up new horizons in a variety fields including synthetic organic supramolecular chemistry. Understanding this bonding situation enables development improved transfer reactions advanced functional materials. Following decade investigations basic principles, range applications now rapidly widening. In Perspective, we assess status field identify its key advances main bottlenecks. Clearing common misunderstandings may hinder future progress, aim inspire direct research efforts.

Language: Английский

Citations

24
Ligand Exchanges Among [N-I+-N] Halogen Bonds: A Robust Strategy for the Construction of Functional Halogen-Bonded Organic Frameworks (XOFs) DOI
Jiahao Zhao, Ning Xia, Zhen‐Nan Tian

et al.

ACS Materials Letters, Journal Year: 2024, Volume and Issue: 6(2), P. 508 - 516

Published: Jan. 3, 2024

The development of diverse linking methods in organic framework materials is crucial for advancing science and engineering. [N-X+-N] halogen bonds are a powerful tool constructing supramolecular aggregates, including halogen-bonded frameworks (XOFs), which have emerged as new class frameworks. However, the existing production XOFs often yields insoluble AgI byproducts, impeding XOF crystallinity, performance, functionality. Hence, alternative preparation required. Here, we present novel approach to 2D via reversible ligand exchange reactions, avoiding unwanted byproducts enhancing crystallinity. Notably, this successfully highly crystalline XOF-TPTE, was unattainable with previous method. XOF-TPTE exhibits exceptional catalytic activity recyclability upon Pd(II) loading, showing remarkable selective performance Heck coupling reactions indicating its potential applications. This method broadens construction horizons expands their

Language: Английский

Citations

10
Pyridine Iodine(I) Cations: Kinetic Trapping as a Sulfonate Complexes DOI Creative Commons
Rakesh Puttreddy, Parveen Kumar, Kari Rissanen

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(16)

Published: Jan. 9, 2024

Seven pyridine iodine(I) sulfonate complexes were prepared and isolated at low temperatures characterized by X-ray diffraction analysis. The inherently instable cations are stabilized an oxygen of anions via the I⋅⋅⋅O halogen bond. In these complexes, iodine atom cation acts as electron acceptor donor. These stable enough in crystalline state, yet decompose rapidly under ambient conditions, also being unstable solution. (pyridine)N-I bond lengths [2.140(3)-2.197(2) Å] bonds [2.345(6)-2.227(3) analogous to (imide)N-I⋅⋅⋅O-N-pyridine uncharged halogen-bonded formed from N-haloimides N-oxides, thus confirming existence elusive cation.

Language: Английский

Citations

4
N−X⋅⋅⋅O−N Halogen Bonds in Complexes of N‐Haloimides and Pyridine‐N‐oxides: A Large Data Set Study DOI Creative Commons
Rakesh Puttreddy, J. Mikko Rautiainen, Shilin Yu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: June 14, 2023

N-X⋅⋅⋅- O-N+ halogen-bonded systems formed by 27 pyridine N-oxides (PyNOs) as halogen-bond (XB) acceptors and two N-halosuccinimides, N-halophthalimides, N-halosaccharins XB donors are studied in silico, solution, the solid state. This large set of data (132 DFT optimized structures, 75 crystal 168 1 H NMR titrations) provides a unique view to structural bonding properties. In computational part, simple electrostatic model (SiElMo) for predicting energies using only properties halogen oxygen is developed. The SiElMo perfect accord with calculated from complexes high-level approaches. Data silico bond single-crystal X-ray structures correlate; however, solution do not. polydentate characteristic PyNOs' atom revealed solid-state attributed lack correlation between DFT/solid-state data. strength slightly affected PyNO [(atomic charge (Q), ionization energy (Is,min ) local negative minima (Vs,min )], σ-hole (Vs,max donor key determinant leading sequence N-halosaccharin>N-halosuccinimide>N-halophthalimide on strength.

Language: Английский

Citations

11
Fluoro and Trifluoromethyl Benzoyl Hypoiodite Complexes with Substituted Pyridines DOI Creative Commons

Václav Kolařík,

Kari Rissanen, Jas S. Ward

et al.

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: 19(13)

Published: April 5, 2024

Based on the prior observation of trifluoroacetate hypoiodite, CF

Language: Английский

Citations

3
Halogen-Bonded [N–I–N]− Complexes with Symmetric or Asymmetric Three-Center–Four-Electron Bonds DOI Creative Commons
Shilin Yu, Khai‐Nghi Truong,

Marcel Siepmann

et al.

Crystal Growth & Design, Journal Year: 2023, Volume and Issue: 23(2), P. 662 - 669

Published: Jan. 23, 2023

A series of LH[Z–I–Z] halogen(I) complexes, where Z = saccharinato or phthalimido anions and LH pyridinium, pyrazinium, tetrabutyl (TBA)- tetramethylammonium (TMA) cations, were prepared, structurally characterized, discussed as complexes consisting a [N–I–N]− anion with three-center–four-electron (3c-4e) halogen bond, hydrogen-bonding (pyridinium pyrazinium) inert (TBA TMA) cation. The symmetric anion, reminiscent the triiodide [I–I–I]− is found to be equivalent its cationic analogue [N–I–N]+ N–I bond lengths 2.26 Å. In contrast homoleptic asymmetry (2.21 2.28 Å) was observed for those which manifested hydrogen only one moiety, thus being analogous asymmetric heteroleptic complexes. results show that 3c-4e [N–I–N] either positively negatively charged, can asymmetrized by an external ([N–I–N]−) using two different ligands (heteroleptic [N–I–N]+).

Language: Английский

Citations

8
Linear bis‐Coordinate Silver(I) and Iodine(I) Complexes with R3R2R1N Tertiary Amines DOI Creative Commons
Parveen Kumar,

Joonas Komulainen,

Antonio Frontera

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(69)

Published: Sept. 8, 2023

Homoleptic [L-I-L]+ iodine(I) complexes (where L is a R3 R2 R1 N tertiary amine) were synthesized via the [L-Ag-L]+ → cation exchange reaction. In solution, amines form [R3 N-Ag-NR1 ]+ silver(I) complexes, which crystallize out from solution as meso-[L-Ag-L]+ characterized by X-ray crystallography. The subsequent analogues extremely reactive and could not be isolated in solid state. Density functional theory (DFT) calculations performed to study Ag+ -N I+ interaction energies with former ranging -80 -100 kJ mol-1 latter -260 -279 . crystal structures revealed ⋅⋅⋅Cπ ⋅⋅⋅H-C short contacts between flexible N-alkyl/N-aryl groups, are first of their kind such precursor complexes.

Language: Английский

Citations

5
Halogen bonding and mechanochemistry combined: synthesis, characterization, and application of N-iodosaccharin pyridine complexes DOI Creative Commons
Christian Schumacher, Khai‐Nghi Truong, Jas S. Ward

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(3), P. 781 - 795

Published: Dec. 5, 2023

Triturating N -iodosaccharin with electron-donating 4-substituted pyridines leads to either charge-neutral XB or cationic iodine( i ) complexes, offering promising alternatives the ubiquitous Barluenga's reagent as electrophilic iodination reagents.

Language: Английский

Citations

5
Iodine(I) and Silver(I) Complexes Incorporating 3-Substituted Pyridines DOI Creative Commons
Kari Rissanen, Jas S. Ward

ACS Omega, Journal Year: 2023, Volume and Issue: 8(26), P. 24064 - 24071

Published: June 21, 2023

Building upon the first report of a 3-acetaminopyridine-based iodine(I) complex (1b) and its unexpected reactivity toward tBuOMe, several new 3-substituted complexes (2b-5b) have been synthesized. The were synthesized from their analogous silver(I) (2a-5a) via to cation exchange reaction, incorporating functionally related substituents as 3-acetaminopyridine in 1b; 3-acetylpyridine (3-Acpy; 2), 3-aminopyridine (3-NH2py; 3), 3-dimethylaminopyridine (3-NMe2py; 4), well strongly electron-withdrawing 3-cyanopyridine (3-CNpy; 5), probe possible limitations formation. individual properties these rare examples pyridines are also compared each other contrasted 4-substituted counterparts which more prevalent literature. While 1b etheric solvents could not be reproduced any analogues herein, was further expanded second solvent. Reaction bis(3-acetaminopyridine)iodine(I) iPr2O gave [3-acetamido-1-(3-iodo-2-methylpentan-2-yl)pyridin-1-ium]PF6 (1d), demonstrated potentially useful C-C C-I bond formation under ambient conditions.

Language: Английский

Citations

4
N−X⋅⋅⋅O−N Halogen Bonds in Complexes of N‐Haloimides and Pyridine‐N‐oxides: A Large Data Set Study DOI Creative Commons
Rakesh Puttreddy, J. Mikko Rautiainen, Shilin Yu

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(34)

Published: June 14, 2023

Abstract N−X⋅⋅⋅ − O−N + halogen‐bonded systems formed by 27 pyridine N‐oxides (PyNOs) as halogen‐bond (XB) acceptors and two N‐halosuccinimides, N‐halophthalimides, N‐halosaccharins XB donors are studied in silico, solution, the solid state. This large set of data (132 DFT optimized structures, 75 crystal 168 1 H NMR titrations) provides a unique view to structural bonding properties. In computational part, simple electrostatic model (SiElMo) for predicting energies using only properties halogen oxygen is developed. The SiElMo perfect accord with calculated from complexes high‐level approaches. Data silico bond single‐crystal X‐ray structures correlate; however, solution do not. polydentate characteristic PyNOs’ atom revealed solid‐state attributed lack correlation between DFT/solid‐state data. strength slightly affected PyNO [(atomic charge (Q), ionization energy (I s,min ) local negative minima (V )], σ‐hole s,max donor key determinant leading sequence N‐halosaccharin>N‐halosuccinimide>N‐halophthalimide on strength.

Language: Английский

Citations

3