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Full-Text Articles in Physical Sciences and Mathematics
Chalcogen Bonding Of Two Ligands To Hypervalent Yf4 (Y=S, Se, Te, Po), Wiktor Zierkiewicz, Rafal Wysokiński, Mariusz Michalczyk, Steve Scheiner
Chalcogen Bonding Of Two Ligands To Hypervalent Yf4 (Y=S, Se, Te, Po), Wiktor Zierkiewicz, Rafal Wysokiński, Mariusz Michalczyk, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
The ability of two NH3 ligands to engage in simultaneous chalcogen bonds to a hypervalent YF4 molecule, with Y=S, Se, Te, Po, is assessed via quantum calculations. The complex can take on one of two different geometries. The cis structure places the two ligands adjacent to one another ina pseudo-octahedral geometry, held there by a pair of σ-hole chalcogen bonds. The bases can also lie nearly opposite one another, in a distorted octahedron containing one π-hole and one strained σ-hole bond. The cis geometry is favored for Y=S, while Te,and Po tend toward the trans structure; they are nearly equally …
Violation Of Electrostatic Rules: Shifting Balance Between Pnicogen Bond And Lone Pair−Π Interaction Tuned By Substituents, Zongqing Chi, Tong Yan, Qing-Zhong Li, Steve Scheiner
Violation Of Electrostatic Rules: Shifting Balance Between Pnicogen Bond And Lone Pair−Π Interaction Tuned By Substituents, Zongqing Chi, Tong Yan, Qing-Zhong Li, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
Complexes were formed pairing ZCl3 (Z=P, As, Sb) with C2R4 (R= H, F, CN). The first interaction present is a pnicogen bond between the Z atom and the C=C π-bond. This bond weakens as the H atoms of ethylene are replaced by electron-withdrawing F and CN and the potential above the alkene switches from negative to positive. In the latter two cases, another set of noncovalent bonds is formed between the Cl lone pairs of ZCl3 and the π*(C=C) antibonding orbital, as well as with the F or CN substituents. The growing strength of these interactions, coupled with a large …
Hexacoordinated Tetrel-Bonded Complexes Between Tf4 (T = Si, Ge, Sn, Pb) And Nch. Competition Between Σ- And Π-Holes, Mariusz Michalczyk, Wiktor Zierkiewicz, Rafal Wysokiński, Steve Scheiner
Hexacoordinated Tetrel-Bonded Complexes Between Tf4 (T = Si, Ge, Sn, Pb) And Nch. Competition Between Σ- And Π-Holes, Mariusz Michalczyk, Wiktor Zierkiewicz, Rafal Wysokiński, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
In order to accommodate the approach of two NCH bases, a tetrahedral TF4 molecule (T=Si,Ge,Sn,Pb) distorts into an octahedral structure in which the two bases can be situated either cis or trans to one another. The square planar geometry of TF4, associated with the trans arrangement of the bases, is higher in energy than its see-saw structure which corresponds to the cis trimer. On the other hand, the square geometry offers an unobstructed path of the bases to the π-holes above and below the tetrel atom so enjoys a higher interaction energy than is the case for the σ-holes approached …