Dipankar Sutradhar

Theoretical study of the O···Cl interaction in fluorinated dimethyl ethers complexed with a Cl atom: is it through a two-center-three-electron bond?

Theoretical investigations are carried out on the interaction between fluorinated dimethyl ethers (FDME, nF = 0-4) and the Cl atom. Short intermolecular O···Cl distances between 2.401 and 2.938 Å reveal the formation of a new class of complexes. The interaction energies calculated with the G2(MP2) method range between -9.1 (nF = 4) and -26.0 (nF = 0) kJ/mol. The charge transfer occurring from the ethers to atomic Cl is moderate and ranges between 0.012 e (nF = 4) to 0.188 e (nF = 0). The binding energies are linearly related to the proton affinity, to the charge transfer (CT) occurring in the molecular system and inversely proportional to the ionization potential and electron affinity (IP-EA) values. The CT and spin density data indicate substantial two-center-three-electron O···Cl interaction in CH3OCH3···Cl and CH3OCH2F···Cl systems, whereas for highly fluorinated ethers the interaction is predominantly electrostatic in nature. The formation of the complex results in a contraction of the CH bonds, especially in the gauche position. The blue shifts of the C-H stretching vibrations calculated in the partially deuterated isotopomers range between 2 and 54 cm(-1) and are correlated to the variation of the CH distances.

A theoretical investigation of the interaction between fluorinated dimethyl ethers and molecular chlorine

Halogen bonds have received a great deal of attention in recent years. In this work, the interaction between fluorinated dimethyl ethers (nF = 0–4) and molecular chlorine has been investigated by the theoretical methods. The two molecules are bonded together by an O···Cl‒Cl halogen bond and the interaction energies calculated at the MP2/aug-cc-pVDZ level range between −15.5 (nF = 0) and −6.1 (nF = 4) kJ mol−1. The correlations between interaction energies and proton affinity or ionisation potential of the ethers are discussed. The interaction between the molecules results in a small contraction of the CH bond of ethers and an elongation of the Cl‒Cl bond. The data are analysed by a natural bond orbital analysis carried out at the wB97XD/6-311++G(d,p) level. The charge transfer from the ethers to Cl2 is weak, ranges between 0.044 and 0.008 e and occurs mainly to the external Cl atom. The elongation of the Cl‒Cl bond is related to the occupation of the σ*(Cl‒Cl) orbital and to the intermolecular hyperconjugation interaction between LP(O) and σ*(Cl‒Cl) orbitals. The interaction between the ethers and chlorine induces an enhancement of the infrared intensity and Raman scattering activity of the ν(Cl‒Cl) vibration.

Strong hyperconjugative interactions in isolated and water complexes of desflurane: a theoretical investigation.

Ab initio MP2/aug-cc-pvDZ and density functional B3LYP calculations with the 6-311++G(d,p) basis set are performed to investigate the conformation of desflurane (CHF2OCHFCF3), its acidity/basicity and its interaction with one water molecule. The calculations include the optimized geometries, the harmonic frequencies of relevant vibrational modes, the binding energies with water, and a detailed natural bond orbital (NBO) analysis Iincluding the NBO charges, the hybridization of the C atoms and the intra- and intermolecular hyperconjugations. The relative energies of the two most stable conformers are discussed as a function of the total hyperconjugative energies resulting from the interaction of lone pairs of the O and F atoms to the different antibonding orbitals of desflurane. The proton affinity is the same for both conformers but the acidity of the CH bond is larger for the less stable conformer. The binding energies of the complexes of two desflurane conformers with one water molecule range from -2.75 to -3.23 kcal mol(-1). Depending on the structure of the complexes, the CH bonds involved in the interaction are contracted or elongated. The σ*(CH) occupation predominates over the hybridization effect in determining the CH bond length. There is an unexpected charge transfer to the external OH bond of the water molecule. This effect is in good agreement with theoretical data on the complexes between fluorinated dimethyl ethers and water and seems to depend on the number of F atoms implanted on the ether molecule.

Theoretical study of the interaction between pyridine derivatives and atomic chlorine. Substituent effect and nature of the bonding

The interaction of pyridine derivatives (H, 4-NH2, 4-CH3, 4-F, 4-CN, 4-NO2) with atomic chlorine is investigated theoretically by the density functional theory (DFT)-based LC-BLYP/aug-cc-pVDZ method. Pyridines and Cl° are held together by a (2c--3e) bond and the intermolecular distances range from 2.313 to 2.343 Å. The existence of a N…Cl bond is confirmed by the atom-in-molecule analysis of the systems. The binding energies of the adducts, ranging from −42.08 to −53.96 kJ mol−1, are linearly correlated to the proton affinity of the pyridines. The charge transfer from pyridine to Cl° varies between 0.222 and 0.277 e. The spin density analysis shows that the strongest complex has the highest (2c–3e) character. The CH bonds are contracted and the ν(CH) vibrations are blueshifted owing to the decrease in σ*(CH) occupation. This decrease results not only from the classical anomeric effect but also from the σ(CC) and σ(CN) → σ*(CH) delocalisation in the heteroaromatic ring.

Unusual Fluorine Substitution Effect on S···Cl Bonding between Sulfides and Atomic Chlorine

A theoretical investigation on the interaction of various sulfides and their fluorinated counterparts (H2S, HSF, F2S, CH3SH, CH3SF, CH2FSH, CH2FSF, NH2SH, NH2SF) with atomic chlorine has been carried out using density functional theory (DFT) based LC-BLYP/aug-cc-pVTZ and sophisticated ab initio CCSD(T)/aug-cc-pVQZ methods. The present study is intended to discuss the influence of the substituents implanted at the sulfur atom on the bonding parameters. The optimized geometries reveal that intermolecular S···Cl distances are short and range between 2.423 and 2.561 Å. A strong contraction of the S-F bond is also predicted. Two-center-three-electron S···Cl bonds are formed; the interaction energies are large and range from -33.9 to -70.1 kJ mol-1. Very surprisingly, the interaction energies are greater and the intermolecular distances are shorter for F-substituted sulfides than for unsubstituted ones. This is in complete contrast with the lower proton affinities and less negative electrostatic potentials of fluorinated sulfides. AIM analysis, the charge transfer from the sulfur atom to the Cl atom, and the spin densities on the Cl and S atoms are considered to explain this unusual behavior. The hyperconjugation energies from the LP(F) to the σ*(S-Cl) antibonding orbital can be considered as one of the stabilizing factors for the greater stability of the fluorinated complexes over the nonfluorinated ones.