SYNTHESES AND CRYSTAL STRUCTURES OF Di-μ-CHLORO-BIS [DITHIOCYANATOSELENATE(II)] AND Di-μ-BROMO-BIS [DITHIOCYANATOSELENATE(II)] SALTS

Hauge, Sverre; Mar⊘y, Kjartan

doi:10.1080/10426500108040245

Cited by 3 publications

(9 citation statements)

References 13 publications

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“…As indicated in the Introduction, alkylthiocyanates are so far poorly studied as chalcogen bond donors and only short contacts of the alkylthiocyanate sulfur with fluorine, , oxygen, − and nitrogen ,, were identified, whereas the NC–(Alk)S···Cl short contacts were not previously reported. Meanwhile, the NC–S···Cl–Se short contacts were noted for the S -coordinated anionic thiocyanate ligand …”

Section: Results and Discussionmentioning

confidence: 99%

“… Another type is the S···Cl chalcogen bond, when chlorine behaves as donor. The latter type of weak interaction is so far represented by only a few examples. ,− In particular, the S···Cl short contacts were recognized between the chloride ligand and sulfur(IV) ,, in SCl 3 + or in metal-coordinated SOCl 2 , between chlorine and sulfur in uncomplexed S 2 Cl 2 and SOCl 2 , between the chloride ligand and thioether or dithiocarbamate ligands in metal species, and between a chloride ligand in metal complexes and sulfur in heterocyclic rings. ,, It is noteworthy that the only one NCS – ···Cl contact involving anionic thiocyanate ligand was reported, and it includes interaction between two dianions [Se 2 (μ-Cl) 2 (SCN) 2 ] 2– …”

Section: Introductionmentioning

confidence: 99%

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Recognition of S···Cl Chalcogen Bonding in Metal-Bound Alkylthiocyanates

Yandanova

Ivanov

Kuznetsov

et al. 2016

Crystal Growth & Design

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Reaction of K2[PtCl4] with excess AlkSCN in water gives the alkylthiocyanate complexes trans-[PtCl2(AlkSCN)2] (Alk = Et 1, n Pr 2; 80–85%). These species were studied, in particular, by X-ray crystallography. In the solid state, both 1 and 2 exhibit the previously unreported S···Cl chalcogen bonding, which consolidates the complexes into networks and leads to layered structures. Theoretical density functional theory calculations and Bader’s atoms in molecules analysis demonstrated two types of intermolecular interactions in tetramer (1)4, viz. the S···Cl chalcogen and the H···Cl hydrogen bonds. Despite that each particular S···Cl or H···Cl bonding is weak with the estimated energy of 1–2 kcal/mol, altogether they play a crucial role in the stabilization of the S2Cl2 fragment in (1)4, the basis set of superposition error corrected interaction energy being −12.8 kcal/mol per monomer complex molecule. The chalcogen bonding and the rhomboidal structure of the S2Cl2 fragment can be interpreted in terms of electrostatic arguments as a result of the interaction between the belt of negative electrostatic potential around the Cl atoms and the sulfur σ-holes. The natural bond orbital analysis revealed that both LP(S) → LP*(Pt)/σ*(Pt–N)/σ*(Pt–Cl) and LP(Cl) → σ*(S–C) types of hyperconjugative charge transfers are important in the chalcogen bonding.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Recognition of S···Cl Chalcogen Bonding in Metal-Bound Alkylthiocyanates

Yandanova

Ivanov

Kuznetsov

et al. 2016

Crystal Growth & Design

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“…(e) References [ 38 , 360 , 382 – 385 ]. (f) References [ 260 , 386 – 389 ]. (g) References [ 390 – 410 ].…”

Section: Methodsmentioning

confidence: 99%

“…(j) References [ 38 , 398 , 419 – 425 ]. (k) Reference [ 386 ]. (l) References [ 398 , 405 , 426 – 433 ].…”

Section: Methodsmentioning

confidence: 99%

“…Differently from S–S–X, the S–Se–X fragments have been found in some dimeric structures with bridging halides [ 383 , 386 ]. Also in these cases the sum of the S–Se and Se–X bond lengths shows elongation (∼19%) with respect to the sum of the covalent radii, and shortening (∼30%) with respect to the sum of the van der Waals radii.…”

Section: Dichalcogen-halidesmentioning

confidence: 99%

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The Nature of the Chemical Bond in Linear Three-Body Systems: From I₃^–to Mixed Chalcogen/Halogen and Trichalcogen Moieties

Aragoni¹,

Arca²,

Devillanova³

et al. 2007

Bioinorganic Chemistry and Applications

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The 3 centre-4 electrons (3c-4e) and the donor/acceptor or charge-transfer models for the description of the chemical bond in linear three-body systems, such as I3 − and related electron-rich (22 shell electrons) systems, are comparatively discussed on the grounds of structural data from a search of the Cambridge Structural Database (CSD). Both models account for a total bond order of 1 in these systems, and while the former fits better symmetric systems, the latter describes better strongly asymmetric situations. The 3c-4e MO scheme shows that any linear system formed by three aligned closed-shell species (24 shell electrons overall) has reason to exist provided that two electrons are removed from it to afford a 22 shell electrons three-body system: all combinations of three closed-shell halides and/or chalcogenides are considered here. A survey of the literature shows that most of these three-body systems exist. With some exceptions, their structural features vary continuously from the symmetric situation showing two equal bonds to very asymmetric situations in which one bond approaches to the value corresponding to a single bond and the second one to the sum of the van der Waals radii of the involved atoms. This indicates that the potential energy surface of these three-body systems is fairly flat, and that the chemical surrounding of the chalcogen/halogen atoms can play an important role in freezing different structural situations; this is well documented for the I3 − anion. The existence of correlations between the two bond distances and more importantly the linearity observed for all these systems, independently on the degree of their asymmetry, support the state of hypervalency of the central atom.

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Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd^II Complexes

et al. 2016

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The reaction of cis-[PdCl(CNXyl)] (Xyl = 2,6-MeCH) with various 1,3-thiazol- and 1,3,4-thiadiazol-2-amines in chloroform gives a mixture of two regioisomeric binuclear diaminocarbene complexes. For 1,3-thiazol-2-amines the isomeric ratio depends on the reaction conditions and kinetically (KRs) or thermodynamically (TRs) controlled regioisomers were obtained at room temperature and on heating, respectively. In CHCl solutions, the isomers are subject to reversible isomerization accompanied with the cleavage of Pd-N and С-N bonds in the carbene fragment XylNCN(R)Xyl. Results of DFT calculations followed by the topological analysis of the electron density distribution within the formalism of Bader's theory (AIM method) reveal that in CHCl solution the relative stability of the regioisomers (∆G = 1.2 kcal/mol; ∆G = 3.2 kcal/mol) is determined by the energy difference between two types of the intramolecular chalcogen bonds, viz. S•••Cl in KRs (2.8-3.0 kcal/mol) and S•••N in TRs (4.6-5.3 kcal/mol). In the case of the 1,3,4-thiadiazol-2-amines, the regioisomers are formed in approximately equal amounts and, accordingly, the energy difference between these species is only 0.1 kcal/mol in terms of ∆G (∆G = 2.1 kcal/mol). The regioisomers were characterized by elemental analyses (C, H, N), HRESI-MS and FTIR, 1D (H, C) and 2D (H,H-COSY, H,H-NOESY, H,C-HSQC, H,C-HMBC) NMR spectroscopies, and structures of six complexes (three KRs and three TRs) were elucidated by single-crystal X-ray diffraction.

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SYNTHESES AND CRYSTAL STRUCTURES OF Di-μ-CHLORO-BIS [DITHIOCYANATOSELENATE(II)] AND Di-μ-BROMO-BIS [DITHIOCYANATOSELENATE(II)] SALTS

Cited by 3 publications

References 13 publications

Recognition of S···Cl Chalcogen Bonding in Metal-Bound Alkylthiocyanates

Recognition of S···Cl Chalcogen Bonding in Metal-Bound Alkylthiocyanates

The Nature of the Chemical Bond in Linear Three-Body Systems: From I₃^–to Mixed Chalcogen/Halogen and Trichalcogen Moieties

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd^II Complexes

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SYNTHESES AND CRYSTAL STRUCTURES OF Di-μ-CHLORO-BIS [DITHIOCYANATOSELENATE(II)] AND Di-μ-BROMO-BIS [DITHIOCYANATOSELENATE(II)] SALTS

Cited by 3 publications

References 13 publications

Recognition of S···Cl Chalcogen Bonding in Metal-Bound Alkylthiocyanates

Recognition of S···Cl Chalcogen Bonding in Metal-Bound Alkylthiocyanates

The Nature of the Chemical Bond in Linear Three-Body Systems: From I3–to Mixed Chalcogen/Halogen and Trichalcogen Moieties

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)PdII Complexes

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Product

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The Nature of the Chemical Bond in Linear Three-Body Systems: From I₃^–to Mixed Chalcogen/Halogen and Trichalcogen Moieties

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd^II Complexes