Substituent effects on the halogen and pnictogen bonds characteristics in ternary complexes 4-YPhNH2···PH2F···ClX (Y = H, F, CN, CHO, NH2, CH3, NO2 and OCH3, and X = F, OH, CN, NC, FCC and NO2): A theoretical study

Tondro, Tahereh; Roohi, Hossein

doi:10.1007/s12039-019-1715-5

Cited by 11 publications

(4 citation statements)

References 84 publications

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“…The aug-cc-pVDZ-PP pseudopotential from the EMSL library , was used for Sb to account for relativistic effects. This level of theory has demonstrated its accuracy and effectiveness in numerous previous studies − of related systems. All geometries were fully optimized and checked to ensure they were true minima, characterized by all positive vibrational frequencies.…”

Section: Systems and Methodsmentioning

confidence: 79%

Coordination of a Central Atom by Multiple Intramolecular Pnicogen Bonds

Scheiner

2020

Inorg. Chem.

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A central pnicogen Z atom (Z = Sb, As) is covalently attached to the O atom of three −O(CH 2 ) n X chains where X represents either an aldehyde or amine group. The chain can fold around so that the basic X group can engage in a noncovalent pnicogen bond with the central Z. The formation of up to three pnicogen bonds is energetically favored. The amine appears to engage in stronger pnicogen bonds than does the aldehyde, and bonds to Sb are favored over As, but there is little dependence on the length of the chain. The formation of each successive pnicogen bond reduces the magnitude of the σ-holes surrounding the Z atom, which tends to weaken the attraction for the basic end of the chain. Article pubs.acs.org/IC

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Section: Systems and Methodsmentioning

confidence: 79%

Coordination of a Central Atom by Multiple Intramolecular Pnicogen Bonds

Scheiner

2020

Inorg. Chem.

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“…All calculations were carried out in the framework of the Gaussian-09 package. The M06-2X DFT functional was applied in conjunction with the aug-cc-pVDZ basis set and with the fourth-row I atom represented by the aug-cc-pVDZ-PP relativistic pseudopotential from the EMSL library. , Numerous previous studies support the accuracy and dependability of this level of theory for related sorts of noncovalent interactions. − The geometries of all species were fully optimized and verified as true minima by the presence of only positive vibrational frequencies. Interaction energies E int are defined as the difference between the energy of the complex and the sum of the two monomers of which it is comprised, holding their internal geometries as in the complex.…”

Section: Systems and Methodsmentioning

confidence: 99%

Proximity Effects of Substituents on Halogen Bond Strength

Lapp

Scheiner

2021

J. Phys. Chem. A

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It is well known that the presence of an electron-withdrawing substituent (EWS) placed near the halogen (X) atom on a Lewis acid molecule amplifies the ability of this unit to engage in a halogen bond with a base. Quantum calculations are applied to examine how quickly these effects fade as the EWS is moved further and further from the X atom. Conjugated alkene and alkyne chains of varying lengths with a terminal C−I first facilitate analysis as to how the number of these multiple bonds affects the strength of CI••N XB to NH 3 . Then, electron-withdrawing F and CN substituents are placed on the opposite end of the chain, and their effects on the XB properties are monitored as a function of their distance from I. These same EWSs are added to the ortho, meta, and para positions of aromatic iodobenzene. It is found that the XB grows in strength as more triple bonds are added to the alkyne, but there is little change caused by elongating an alkene. The cyano group has a much stronger effect than does F. While F strengthens the XB, its effects are quickly attenuated as it is moved further from I. The consequences of CN substitution are stronger and extend over a longer distance. Placement of an EWS on the phenyl ring diminishes with distance: o > m > p, and the effects of disubstitution are nearly additive. These trends apply not only to energetics but also to geometries, properties of the wave function, σ-hole depth, and NMR shielding.

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“…A relatively new congener of noncovalent interactions is the pnictogen bond (PnB), − which (in analogy with the IUPAC definition of a halogen bond) can be defined as an attractive interaction between the electron-deficient region of a pnictogen (group 15 element) called a pnictogen bond donor and a Lewis base (pnictogen bond acceptor, acting as an electron pair donor) . In the past few years, the potential of PnB in structural assembly, supramolecular architecture, anion sensing, (organo)catalysis, and molecular recognition has also been highlighted. ,− On the basis of thorough computational studies, ,,− pnictogen bonding is chiefly electrostatic in nature (attraction between the oppositely charged regions around the two centers). Moreover, charge transfer effects (donation from the lone pair of the Lewis base into the σ*-antibonding orbitals at the pnictogen center) may also contribute, though to a much lesser extent.…”

Section: Introductionmentioning

confidence: 99%

Tweaking the Charge Transfer: Bonding Analysis of Bismuth(III) Complexes with a Flexidentate Phosphane Ligand

et al. 2020

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To account for the charge transfer and covalent character in bonding between P and Bi centers, the electronic structures of [P(C 6 H 4 - o -CH 2 SCH 3 ) 3 BiCl n ] (3– n )+ ( n = 0–3) model species have been investigated computationally. On the basis of this survey a synthetic target compound with a dative P→Bi bond has been selected. Consecutively, the highly reactive bismuth cage [P(C 6 H 4 - o -CH 2 SCH 3 ) 3 Bi] 3+ has been accessed experimentally and characterized. Importantly, our experiments (single-crystal X-ray diffraction and solid-state NMR spectroscopy) and computations (NBO and AIM analysis) reveal that the P···Bi bonding in this trication can be described as a dative bond. Here we have shown that our accordion-like molecular framework allows for tuning of the interaction between P and Bi centers.

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Substituent effects on the halogen and pnictogen bonds characteristics in ternary complexes 4-YPhNH2···PH2F···ClX (Y = H, F, CN, CHO, NH2, CH3, NO2 and OCH3, and X = F, OH, CN, NC, FCC and NO2): A theoretical study

Cited by 11 publications

References 84 publications

Coordination of a Central Atom by Multiple Intramolecular Pnicogen Bonds

Coordination of a Central Atom by Multiple Intramolecular Pnicogen Bonds

Proximity Effects of Substituents on Halogen Bond Strength

Tweaking the Charge Transfer: Bonding Analysis of Bismuth(III) Complexes with a Flexidentate Phosphane Ligand

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