Theoretical study of the red‐ and blue‐shifted hydrogen bonds of nitroxyl and acetylene dimers

Liu, Ying; Liu, Wenqing; Yang, Yong; Liu, Jianguo

doi:10.1002/qua.21000

Cited by 23 publications

(21 citation statements)

References 29 publications

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“…[345][346][347][348][349] In the specific case of the formation of traditional hydrogen-bonded complexes, the variations in charge density provoke the appearance of red-and blue-shifts in the infrared spectrum often related to the proton donors. [350][351][352][353][354][355][356][357] Hitherto, the quantification of the charge transfer is fundamental in this regard [358][359][360][361][362][363][364] because these vibrational phenomena are immediate consequences of the drastic structural deformations in both proton donors and acceptors following complexation. [365][366][367] One interesting example of deformation on monoprotic acids is related to their bond lengths, [368][369] Fig.…”

Section: Vibrational Red-and Blue-shifts In Intermolecular Interactionsmentioning

confidence: 99%

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Oliveira

2013

Phys. Chem. Chem. Phys.

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In this paper, the intermolecular structural study asserted by the vibrational analysis in the stretch frequencies of hydrogen bonds (π···H) and dihydrogen bonds (H(-δ)···H(+δ)) have definitively been revisited by means of calculations carried out by Density Functional Theory (DFT) and topological parameters derived from the classic treatise of the Quantum Theory of Atoms in Molecules (QTAIM). As a matter of fact the π···H hydrogen bond is formed between the hydrofluoric acid and the C≡C bond of the acetylene, but the QTAIM calculations revealed a distortion in this interaction due to the formation of the ternary complex C(2)H(2)···2(HF). Although the π bonds of ethylene (C(2)H(4)), propylene (C(2)H(3)(CH(3))), and t-butylene (C(2)H(2)(CH(3))(2)) are considered proton acceptors, two hydrogen-bond types--π···H and C···H--can be observed. Over and above the analysis of the π hydrogen bonds, theoretical arguments also were used to discuss the red-shifts in the stretch frequencies of the binary dihydrogen complexes formed by BeH(2)···HX with X = F, Cl, CN, and CCH. Although a vibrational blue-shift in the stretch frequency of the H-C bond of HCF(3) due to the formation of the BeH(2)···HCF(3) dihydrogen complex was obtained, unmistakable red-shifts were detected in LiH···HCF(3), MgH(2)···HCF(3), and NaH···HCF(3). Moreover, the alkali-halogen bonds were identified in relation to the formation of the trimolecular systems NaH···2(HCF(3)) and NaH···2(HCCl(3)). At last, theoretical calculations and QTAIM molecular integrations were used to study a novel class of dihydrogen-bonded complexes (mC(2)H(5)(+)···nMgH(2) with m = 1 or 2 and n = 1 or 2) based in the insight that MgH(2) can bind with the non-localized hydrogen H(+δ) of the ethyl cation (C(2)H(5)(+)). In an overview, QTAIM calculations were applied to evaluate the molecular topography, charge density, as well as to interpret the shifted frequencies either to red or blue caused by the formation of the hydrogen bonds and dihydrogen bonds.

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Section: Vibrational Red-and Blue-shifts In Intermolecular Interactionsmentioning

confidence: 99%

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Oliveira

2013

Phys. Chem. Chem. Phys.

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“…HNO can form various kinds of complexes with non-metal molecules, such as CO [31], HNO [32,33], HOX (X = F, Cl, Br, I) [34], CH 3 X (X = F, Cl, Br) [35], HFSO 2 [36], CH 3 CHO [37], HCONH 2 [38], XCHY (X = H, F, Cl, Br, CH 3 ; Y = O, S) [39], C 2 H 2 [40], HArF [41], and O 3 [42]. Based on the computational investigations, it is interesting to note that in these complexes, as long as the geometries allow, the most stable isomers prefer to involve both the terminal H and O atoms of HNO in the interactions, as illustrated in Fig.…”

Section: Interactions Between Hno and Non-metal Moleculesmentioning

confidence: 99%

Computational investigations of HNO in biology

Zhang

2013

Journal of Inorganic Biochemistry

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HNO (nitroxyl) has been found to have many physiological effects in numerous biological processes. Computational investigations have been employed to help understand the structural properties of HNO complexes and HNO reactivities in some interesting biologically relevant systems. The following computational aspects were reviewed in this work: 1) structural and energetic properties of HNO isomers; 2) interactions between HNO and non-metal molecules; 3) structural and spectroscopic properties of HNO metal complexes; 4) HNO reactions with biologically important non-metal systems; 5) involvement of HNO in reactions of metal complexes and metalloproteins. Results indicate that computational investigations are very helpful to elucidate interesting experimental phenomena and provide new insights into unique structural, spectroscopic, and mechanistic properties of HNO involvement in biology.

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“…There are indeed numerous reports on intermolecular complexes in which HNO has been shown to display blue-shifted N-H stretching frequencies. [38][39][40][41][42] Large blue shifts have also been predicted for complexes of HSN with H 2 O, HF, fluoromethanes 25 and amines. 43 All the others have negative k A-X,A-H , with the exception of HNS, which turned out to be a borderline case.…”

Section: Vicinal Coupling Constantsmentioning

confidence: 85%

Blue-shifted A–H stretching frequencies in complexes with methanol: the decisive role of intramolecular coupling

Karpfen

2011

Phys. Chem. Chem. Phys.

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The presence of a blue shift of A-H stretching frequencies in intermolecular complexes is directly related to the intramolecular coupling between A-H and vicinal A-X bonds in isolated molecules. The intramolecular coupling between vicinal bonds is the decisive parameter that determines whether a general molecule is a candidate for displaying blue-shifted A-H stretching frequencies in intermolecular complexes, with or without hydrogen bonding. The structures and vibrational spectra of dimeric complexes of methanol with H(2)O, HF, HCN, HNC, HOF, HNO, and HSN are investigated at the MP2/6-311++G(2d,2p) approach. Blue- and red-shifts of the methyl C-H stretches of methanol and the various other A-H stretching frequencies in the complexes can be predicted by normal coordinate analyses of methanol and the partner molecules. It is, hence, suggested that conventional normal coordinate analysis is the appropriate predictive tool to decide beforehand whether a given molecule is a promising candidate for the observation of blue shifts in intermolecular complexes.

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Theoretical study of the red‐ and blue‐shifted hydrogen bonds of nitroxyl and acetylene dimers

Cited by 23 publications

References 29 publications

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Computational investigations of HNO in biology

Blue-shifted A–H stretching frequencies in complexes with methanol: the decisive role of intramolecular coupling

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Theoretical study of the red‐ and blue‐shifted hydrogen bonds of nitroxyl and acetylene dimers

Cited by 23 publications

References 29 publications

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H−δ⋯H+δdihydrogen bonds

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H−δ⋯H+δdihydrogen bonds

Computational investigations of HNO in biology

Blue-shifted A–H stretching frequencies in complexes with methanol: the decisive role of intramolecular coupling

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Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds