Pnicogen Bonds: A New Molecular Linker?

Zahn, Stefan; Frank, René; Hey-Hawkins, E.; Kirchner, Barbara

doi:10.1002/chem.201002146

Cited by 407 publications

(313 citation statements)

References 58 publications

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“…Unfortunately, while extremely useful for characterizing covalent bonding, ELF only recognizes non-covalent interactions arising from strong electrostatic forces, mainly those occurring in hydrogen bonds, 162,163 halogen bonds, 164,165 and pnicogen bonds. 166 Given that each of the above tools fails to properly describe weak non-covalent interactions, it becomes necessary to search for an alternative approach elsewhere. If one concedes that the electron density does contain all the relevant information about a system, then an attractive possibility is look at the density topology, i.e., the density's gradient field and Hessian.…”

Section: Visualization Toolsmentioning

confidence: 99%

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

105

102

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Today's quantum chemistry methods are extremely powerful but rely upon complex quantities such as the massively multidimensional wavefunction or even the simpler electron density. Consequently, chemical insight and a chemist's intuition are often lost in this complexity leaving the results obtained difficult to rationalize. To handle this overabundance of information, computational chemists have developed tools and methodologies that assist in composing a more intuitive picture that permits better understanding of the intricacies of chemical behavior. In particular, the fundamental comprehension of phenomena governed by non-covalent interactions is not easily achieved in terms of either the total wavefunction or the total electron density, but can be accomplished using more informative quantities. This perspective provides an overview of these tools and methods that have been specifically developed or used to analyze, identify, quantify, and visualize non-covalent interactions. These include the quantitative energy decomposition analysis schemes and the more qualitative class of approaches such as the Non-covalent Interaction index, the Density Overlap Region Indicator, or quantum theory of atoms in molecules. Aside from the enhanced knowledge gained from these schemes, their strengths, limitations, as well as a roadmap for expanding their capabilities are emphasized. ©2017Author(s

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Section: Visualization Toolsmentioning

confidence: 99%

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

105

102

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“…In the SCS···Cl − system, the bonded C=S group contracts by 2.3 mÅ [35], while in the SCS···OClH system, the bonded C=S group elongates by 3 mÅ [38]. In the chalcogen bond formed between Se=C=Se and water, the elongation of the free C=Se bond is larger (3 mÅ) than the elongation of the bonded C=Se group (1 mÅ) but a reverse trend is predicted when Se=C=Se interacts with electron donors such as PH 3 or H 2 S [60]. These data indicate that the variation of the C=S distances induced by the interaction with electron donors is small.…”

Section: Nbo Analysismentioning

confidence: 99%

“…Depending on the nature of the bridging atoms [1][2][3], these interactions are commonly designed as halogen [4][5][6][7][8][9], chalcogen [10][11][12][13][14][15][16] or pnicogen [17][18][19][20] bonds. The attractive force has been attributed to an anisotropic distribution of electron density around the bridging X atom, characterized by a crown of positive electrostatic potential along the extension of the Y-X bond (σ-hole) or in areas perpendicular to it (π-hole) [6-8, 21, 22].…”

Section: Introductionmentioning

confidence: 99%

Ab initio and DFT studies of the interaction between carbonyl and thiocarbonyl groups: the role of S···O chalcogen bonds

et al. 2016

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“…The hydrogen [1,2], halogen [3][4][5][6][7][8][9][10], chalcogen [11][12][13][14][15][16][17][18][19][20][21][22][23][24], pnictogen [25][26][27][28][29][30][31], tetrel [32] bonding, stacking [33][34][35][36][37], cation/anion-π [38][39][40][41][42], and metallophilic interactions [43][44][45] play key roles in many chemical, physical, and biochemical processes, due to their ability to control structures and properties of associates and supramolecular systems.…”

Section: Introductionmentioning

confidence: 99%

Intra-/Intermolecular Bifurcated Chalcogen Bonding in Crystal Structure of Thiazole/Thiadiazole Derived Binuclear (Diaminocarbene)PdII Complexes

et al. 2018

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The coupling of cis-[PdCl2(CNXyl)2] (Xyl = 2,6-Me2C6H3) with 4-phenylthiazol-2-amine in molar ratio 2:3 at RT in CH2Cl2 leads to binuclear (diaminocarbene)PdII complex 3c. The complex was characterized by HRESI+-MS, 1H NMR spectroscopy, and its structure was elucidated by single-crystal XRD. Inspection of the XRD data for 3c and for three relevant earlier obtained thiazole/thiadiazole derived binuclear diaminocarbene complexes (3a EYOVIZ; 3b: EYOWAS; 3d: EYOVOF) suggests that the structures of all these species exhibit intra-/intermolecular bifurcated chalcogen bonding (BCB). The obtained data indicate the presence of intramolecular S•••Cl chalcogen bonds in all of the structures, whereas varying of substituent in the 4th and 5th positions of the thiazaheterocyclic fragment leads to changes of the intermolecular chalcogen bonding type, viz. S•••π in 3a,b, S•••S in 3c, and S•••O in 3d. At the same time, the change of heterocyclic system (from 1,3-thiazole to 1,3,4-thiadiazole) does not affect the pattern of non-covalent interactions. Presence of such intermolecular chalcogen bonding leads to the formation of one-dimensional (1D) polymeric chains (for 3a,b), dimeric associates (for 3c), or the fixation of an acetone molecule in the hollow between two diaminocarbene complexes (for 3d) in the solid state. The Hirshfeld surface analysis for the studied X-ray structures estimated the contributions of intermolecular chalcogen bonds in crystal packing of 3a–d: S•••π (3a: 2.4%; 3b: 2.4%), S•••S (3c: less 1%), S•••O (3d: less 1%). The additionally performed DFT calculations, followed by the topological analysis of the electron density distribution within the framework of Bader’s theory (AIM method), confirm the presence of intra-/intermolecular BCB S•••Cl/S•••S in dimer of 3c taken as a model system (solid state geometry). The AIM analysis demonstrates the presence of appropriate bond critical points for these interactions and defines their strength from 0.9 to 2.8 kcal/mol indicating their attractive nature.

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Pnicogen Bonds: A New Molecular Linker?

Cited by 407 publications

References 58 publications

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Ab initio and DFT studies of the interaction between carbonyl and thiocarbonyl groups: the role of S···O chalcogen bonds

Intra-/Intermolecular Bifurcated Chalcogen Bonding in Crystal Structure of Thiazole/Thiadiazole Derived Binuclear (Diaminocarbene)PdII Complexes

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