Three-Center, Four-Electron Bonding and Structural Characteristics of Two-Coordinate Iodine(I) Complexes with Halogen and Chalcogen Ligands. Synthesis, Spectroscopic Characterization and X-Ray Structural Studies of (Triiodo)[tris(dimethylamino)phosphaneselenide]iodine(I) and Bis{(triiodo)[tri(N-morpholyl)phosphaneselenide]iodine(I)}/Diiodine Molecular Complex.

Rudd, Martin D.; Lindeman, Sergey V.; Husebye, Steinar; Persson, Ola; Robinson, Ward T.; Roos, Björn O.; Vallance, Claire; Wood, Bryan R.

doi:10.3891/acta.chem.scand.51-0689

Cited by 48 publications

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“…[14b, 22,23] For this, a wide survey of the reactivity of different chalcogenone donors featuring > C = E (E= S, Se) groups towards dihalogens and interhalogens under different experimental conditions is necessary.…”

Section: Resultsmentioning

confidence: 99%

“…In fact, by using a 1: 4 + cation (E = S, Se; X = I, Br), which can undergo attack from an appropriate nucleophile either on the chalcogen or halogen site. [22] If the nucleophilic species is a chalcogenone donor, both a […”

Section: Resultsmentioning

confidence: 99%

“…In the case of X À as nucleophilic species, CT and "T-shaped" hypervalent adducts are possible as products. [22] Whether this cation really forms in solution has not been proved in all cases considered, but it has been observed that the charge distribution calculated on [> CÀEÀX]…”

Section: Resultsmentioning

confidence: 99%

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A Unique Case of Oxidative Addition of Interhalogens IX (X=Cl, Br) to Organodiselone Ligands: Nature of the Chemical Bonding in Asymmetric ISeX Polarised Hypervalent Systems

Juárez-Pérez

Aragoni

Arca

et al. 2011

Chemistry A European J

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The reactivity of the imidazoline-2-selone derivatives 1,1'-methylenebis(3-methyl-4-imidazoline-2-selone) (D1) and 1,2-ethylenebis(3-methyl-4-imidazoline-2-selone) (D2) towards the interhalogens IBr and ICl has been investigated in the solid state with the aim of synthesising "T-shaped" hypervalent chalcogen compounds featuring the extremely rare linear asymmetric I-E-X moieties (E=S, Se; X=Br, Cl). X-ray diffraction analysis and FT-Raman measurements provided a clear indication of the presence in the compounds obtained of discrete molecular adducts containing I-Se-Br and I-Se-Cl hypervalent moieties following a unique oxidative addition of interhalogens IX (X=Cl, Br) to the organoselone ligands. In all asymmetric hypervalent systems isolated, a strong polarisation was observed, with longer bond lengths at the selenium atom involving the most electronegative halogen. A topological electron density analysis on model compounds based on the quantum theory of atoms-in-molecules (QTAIM) and electron localisation function (ELF) established the three-centre-four-electron (3c-4e) nature of the bonding in these very polarised selenium hypervalent systems and new criteria were suggested to define and ascertain the hypervalency of the selenium atoms in these and related halogen and interhalogen adducts.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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A Unique Case of Oxidative Addition of Interhalogens IX (X=Cl, Br) to Organodiselone Ligands: Nature of the Chemical Bonding in Asymmetric ISeX Polarised Hypervalent Systems

Juárez-Pérez

Aragoni

Arca

et al. 2011

Chemistry A European J

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“…The experimental data in Figures 4 and 5, except those for adducts characterized by bridging molecules (E−I distances lying between 3.01 and 3.30 Å and I−I distances between 2.74 and 2.79 Å, = , ) [65] and the data for the adduct benzimidazole-2(3)-thione· [45], can be fitted very well to the equation [66]

Δ d (I - Y) = - b_{1} ln {1 - \exp [\frac{(d_{0} (E - I) - d (E - I))}{b_{2}}]}

obtainable by assuming a valence (bond order) model for the description of the E−I−Y system within CT adducts, with n (I−Y) + n (E−I) = 1 ( = , ; n = bond order) [12, 77], with d 0 (E−I) = 2.396 Å and 2.528 Å (experimental values for = , and , resp) [12], b 1 and b 2 are parameters.…”

Section: Discussionmentioning

confidence: 99%

“…This variety of products, besides being very puzzling from a kinetic and thermodynamic point of view [66, 77, 88, 89, 93], represents a serious challenge when it comes to characterize the outcome of the reactions between chalcogen-donor ligands and dihalogens and interhalogens, especially when an X-ray crystal structure determination is not possible. The FT-Raman spectroscopy was proved to be of particular help in giving qualitative structural information particularly in the case of compounds from reactions with diiodine [65].…”

Section: Introductionmentioning

confidence: 99%

Reactions Between Chalcogen Donors and Dihalogens/Interalogens: Typology of Products and Their Characterization by FT‐Raman Spectroscopy

Arca

Aragoni²,

Devillanova³

et al. 2006

Bioinorganic Chemistry and Applications

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Mechanistic Aspects of the Reaction between Br2 and Chalcogenone Donors (LE; E=S, Se): Competitive Formation of 10-E-3, T-Shaped 1:1 Molecular Adducts, Charge-Transfer Adducts, and [(LE)2]2+ Dications

Aragoni¹,

Arca²,

Demartin

et al. 2001

Chem. Eur. J.

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The synthesis and spectroscopic characterisation of the products obtained by treatment of N,N'-dimethylimidazolidine-2-thione (1), N,N'-dimethylimidazolidine-2-selone (2), N,N'-dimethylbenzoimidazole-2-thione (3) and N,N'-dimethylbenzoimidazole-2-selone (4) with Br2 in MeCN are reported, together with the crystal structures of the 10-E-3, T-shaped adducts 2 . Br2 (12), 3 . Br2 (13) and 4 . Br2 (14). A conductometric and spectrophotometric investigation into the reaction between 1-4 and Br2, carried out in MeCN, allows the equilibria involved in the formation of the isolated 10-E-3 (E = S, Se) hypervalent compounds to be hypothesised. In order to understand the reasons why S and Se donors can give different product types on treatment with Br2 and I2, DFT calculations have been carried out on 1-8, 19 and 20, and on their corresponding hypothetical [LEX]+ cations (L = organic framework; E = S, Se; X = Br, I), which are considered to be key intermediates in the formation of the different products. The results obtained in terms of NBO charge distribution on [LEX]+ species explain the different behaviour of 1-8, 19 and 20 in their reactions with Br2 and I2 fairly well. X-ray diffraction studies show 12-14 to have a T-shaped (10-E-3; E = S, Se) hypervalent chalcogen nature. They contain an almost linear Br-E-Br (E = S, Se) system roughly perpendicular to the average plane of the organic molecules. In 12, the Se atom of each adduct molecule has a short interaction with the Br(1) atom of an adjacent unit, such that the Se atom displays a roughly square planar coordination. The Se-Br distances are asymmetric [2.529(1) vs. 2.608(1) A], the shorter distance being that with the Br(1) atom involved in the short intermolecular contact. In contrast, in the molecular adducts 13 and 14, which lie on a two-fold crystallographic axis, the Br-E-Br system is symmetric and no short intermolecular interactions involving chalcogen and bromine atoms are observed. The adducts are arranged in parallel planes; this gives rise to a graphite-like stacking. The new crystalline modification of 10, obtained from acetonitrile solution, confirms the importance of short intermolecular contacts in determining the asymmetry of Br-E-Br (E = S, Se) and I-Se-I groups in hypervalent 10-E-3 compounds. The analogies in the conductometric and spectrophotometric titrations of 1 and 2-4 with Br2, together with the similarity of the vibrational spectra of 11-14, also imply a T-shaped nature for 11. The vibrational properties of the Br-E-Br (E = S, Se) systems resemble those of the Br3- and IBr2- anions: the Raman spectrum of a symmetric Br-E-Br group shows only one peak near 160 cm(-1), as found for symmetric Br3- and IBr2- anions, while asymmetric Br-E-Br groups also show an antisymmetric Br-E-Br mode at around 190 cm(-1), as observed for asymmetric Br3- and IBr2- ions. Therefore, simple IR and Raman measurements provide a useful tool for distinguishing between symmetric and asymmetric Br-E-Br groups, and hence allow predictions about the crystal packing of th...

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Cited by 48 publications

References 0 publications

A Unique Case of Oxidative Addition of Interhalogens IX (X=Cl, Br) to Organodiselone Ligands: Nature of the Chemical Bonding in Asymmetric ISeX Polarised Hypervalent Systems

A Unique Case of Oxidative Addition of Interhalogens IX (X=Cl, Br) to Organodiselone Ligands: Nature of the Chemical Bonding in Asymmetric ISeX Polarised Hypervalent Systems

Reactions Between Chalcogen Donors and Dihalogens/Interalogens: Typology of Products and Their Characterization by FT‐Raman Spectroscopy

Mechanistic Aspects of the Reaction between Br2 and Chalcogenone Donors (LE; E=S, Se): Competitive Formation of 10-E-3, T-Shaped 1:1 Molecular Adducts, Charge-Transfer Adducts, and [(LE)2]2+ Dications

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