Intermolecular C-H∙∙∙H-M dihydrogen bonds in five-membered heterocyclic complexes: a DFT and ab-initio study

Duraisamy, P.; Gopalan, Praveena; Angamuthu, Abiram

doi:10.1007/s00706-020-02680-9

Cited by 7 publications

(2 citation statements)

References 67 publications

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“…The topological maps of the stable hydrated N 2 O complexes are shown in Fig. 7, in which the green color represents the BCPs, red color balls represent the ring critical points (RCPs) and Y represents the cage critical points (CCPs) [57][58][59]. It is evident from the topological map N 2 O interacts with the water molecules which gives rise to (i…”

Section: Qtaim and Nci-rdg Analysismentioning

confidence: 99%

Theoretical insights into the structure, stability, thermochemistry, and bonding in hydrated N2O clusters

Manogaran,

Ambigapathy,

Pandiaraj

et al. 2023

Preprint

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We have investigated the structure, stability, thermochemistry, and bonding in microhydrated N2O clusters (N2O‧Wn (n = 1–12)). To do this we used various theoretical methods and techniques including density functional theory (DFT), quantitative molecular electrostatic potential surface (MESP), quantum theory of atoms in molecules (QTAIM), and noncovalent interaction analysis (NCI). A detailed density functional search shows that N2O lies on the top of the water molecules and water molecules tend to form a cage structure. The existence of water in cage geometry and segregation of N2O unveils the presence of weak bonding between N2O and water cluster. The computed adsorption energy (ΔEabs), association energy (AE), and incremental association energy (ΔEIA) were all negative which means the complexes are stabilized. In small size clusters the most stable isomer dominates the relative population at all temperatures. In cluster with 6 and more water all the isomers contribute at the high atmospheric temperature. The formation of all the hydrated N2O complexes is enthalpically favored over the range of atmospheric altitudes. In general, the free energy change and enthalpy change decrease with the increase in altitude. The enthalpy change for the clusters unveils a distinct inflection at the tropopause. MESP analysis shows a higher Vs,max value on the hydrogen atom of a water molecule at the terminal end which helps for the addition of water molecules. QTAIM and NCI analyses reveal that N2O-water complexes are predominately stabilized by weak noncovalent interactions like N‧‧‧OW, O‧‧‧Ow, and O‧‧‧Hw. Overall, this work helps in understanding the structure, and stability of hydrated N2O molecules at different altitudes of the atmosphere.

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Section: Qtaim and Nci-rdg Analysismentioning

confidence: 99%

Theoretical insights into the structure, stability, thermochemistry, and bonding in hydrated N2O clusters

Manogaran,

Ambigapathy,

Pandiaraj

et al. 2023

Preprint

View full text Add to dashboard Cite

show abstract

“…Noncovalent interactions play a crucial role in many branches of physical and chemical science [1][2][3]. Among these interactions, dihydrogen bond (DHB) has been presented as an unconventional hydrogen bond between two opposite charged hydrogen atoms [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

Excited state dynamics of P-H···H-B and P-H···H-Si hydride-hydride interactions and potential dehydrogenation reactions in frustrated lewis pair

Yang,

Zhang,

Ding

et al. 2024

Phys. Scr.

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Dihydrogen interactions plays a crucial role in frustrated Lewis pairs (FLPs) strategy and promotes dehydrogenation reactions due to its low directionality and saturability. This work focuses on the excited-state dynamics of the P-H···H-B and P-H···H-Si intramolecular hydride-hydride interactions in 4-bis(pentafluorophenyl)-borane-5-dimesitylphosphino-9,9-dimethylxanthine (FPB-MP-MX) and 5-dimethylsilyl-9,9-dimethylxanthene-4-yl-diphenylphosphonium cation (MSi-PP-MX), respectively. The interaction between B-H, C-H and π electron of benzene ring are also considered. Upon photoexcitation to the first singlet (S1) state, the P-H···H-B of FPB-MP-MX and the P-H···H-Si of MSi-PP-MX are both strengthened, while B-H···π and C−H···π interaction are all weakened. These changes are induced by the charge transfer from the 9,9-dimethyl-xanthene moiety to the electron-deficient phosphorus cation and mesitylene group, which are demonstrated by the molecule orbital, electron-hole, and charge analysis. In addition, the potential energy curve of FPB-MP-MX scanned the P-H···H-B shows low energy barriers of 20.68 kcal/mol in the S0 state, implying the potential dehydrogenation reaction with lower energy of hydrogen product. In contrast to FPB-MP-MX, the potential energy curve of MSi-PP-MX scanned the P-H···H-Si has large energy barrier of 42.66 kcal/mol in the S0 state and 32.01 kcal/mol in the S1 state, which demonstrates the difficulty of dehydrogenation reaction. This works presents reasonable interpretation on the dynamics changes of dihydrogen bonding and dehydrogenation reaction of frustrated Lewis pairs upon photoexcitation.

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Effect of boron halogenation on dihydrogen bonds: A quantum mechanical approach

Arumugam,

Angamuthu,

Gopalan

2024

J Chem Sci

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Intermolecular C-H∙∙∙H-M dihydrogen bonds in five-membered heterocyclic complexes: a DFT and ab-initio study

Cited by 7 publications

References 67 publications

Theoretical insights into the structure, stability, thermochemistry, and bonding in hydrated N2O clusters

Theoretical insights into the structure, stability, thermochemistry, and bonding in hydrated N2O clusters

Excited state dynamics of P-H···H-B and P-H···H-Si hydride-hydride interactions and potential dehydrogenation reactions in frustrated lewis pair

Effect of boron halogenation on dihydrogen bonds: A quantum mechanical approach

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