DFT studies and AIM analysis of intramolecular N–H···O hydrogen bonds in 3-aminomethylene-2 methoxy-5,6-dimethyl-2-oxo-2,3-dihydro-2λ5-[1,2]oxaphosphinin-4-one and its derivatives

Małecka, Magdalena

doi:10.1007/s11224-009-9556-3

Cited by 25 publications

(22 citation statements)

References 56 publications

(73 reference statements)

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“…C1-C2 and N4-C5 as formal single bonds have small values of ellipticity comparable to known literature [70][71][72]. N-C3 in nmur moiety may be considered as double ones with e BCP about 0.2.…”

Section: Discussionsupporting

confidence: 83%

Co-crystal/salt crystal structure disorder of trichloroacetic acid–N-methylurea complex with double system of homo- and heteronuclear O–H···O/N–H···O hydrogen bonds: X-ray investigation, ab initio and DFT studies

Rybarczyk‐Pirek

2012

Struct Chem

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The X-ray diffraction studies revealed disorder of a trichloroacetic acid-N-methylurea complex crystal structure, connected with a proton transfer via O-HÁÁÁO hydrogen bond. The observed structure corresponds to a co-existence of ionic (salt) and neutral (co-crystal) forms of the complex in the solid state in ratio 3:1, respectively. The geometrical analysis based on ab initio and density functional theory methods combined with the experimental research indicated that two different N-methylurea molecular conformations, defined by CNCN torsion angle, correspond to the neutral and the ionic form of the complex, respectively. The conformational changes seem to be connected with stabilization of the ionic structure after a proton transfer, as according to theoretical calculations this form of the complex (the ionic one) was unstable in the gas phase. A particular attention was focused on a system of a double intermolecular hydrogen bonds, O-HÁÁÁO and N-HÁÁÁO which join molecules into the title complex. The analysis of these interactions performed in terms of their geometry, energetic and topological electron density properties let for their classification into strong and medium strength hydrogen bonds. It was also found that the antibonding hydrogen bonding donor orbital occupation corresponded to the stabilization energy resulting from charge transfer in hydrogen bonds. Hence, it is postulated as a possible indicator of interaction strength.

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Section: Discussionsupporting

confidence: 83%

Co-crystal/salt crystal structure disorder of trichloroacetic acid–N-methylurea complex with double system of homo- and heteronuclear O–H···O/N–H···O hydrogen bonds: X-ray investigation, ab initio and DFT studies

Rybarczyk‐Pirek

2012

Struct Chem

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“…Thus the N À H bonds have similar values of 1 (0.329) and r 2 1 (À1.763) at the BCP of NÀH bonds in organic systems examined at the B3LYP/6-311++G** level of theory. [41] Recently, a topological analysis of N 2 À CuX systems and Cu À X bonds has been carried out in which X = Cl, Br, or F at the B3LYP/6-311+G(2d)//MP2A C H T U N G T R E N N U N G (full)/6-311+GA C H T U N G T R E N N U N G (2df) level of theory. [42] Although the basis sets used in this study are slightly different from our choice of basis sets, the numerical values of 1 and r 2 1 at the CuÀX bonds are similar and the trends upon changing X from F to Cl are the same.…”

Section: Mononuclear Model Systemsmentioning

confidence: 99%

The Nature of Bond Critical Points in Dinuclear Copper(I) Complexes

Dinda

Samuelson

2012

Chemistry A European J

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Closed-shell contacts between two copper(I) ions are expected to be repulsive. However, such contacts are quite frequent and are well documented. Crystallographic characterization of such contacts in unsupported and bridged multinuclear copper(I) complexes has repeatedly invited debates on the existence of cuprophilicity. Recent developments in the application of Bader's theory of atoms-in-molecules (AIM) to systems in which weak hydrogen bonds are involved suggests that the copper(I)-copper(I) contacts would benefit from a similar analysis. Thus the nature of electron-density distributions in copper(I) dimers that are unsupported, and those that are bridged, have been examined. A comparison of complexes that are dimers of symmetrical monomers and those that are dimers of two copper(I) monomers with different coordination spheres has also been made. AIM analysis shows that a bond critical point (BCP) between two Cu atoms is present in most cases. The nature of the BCP in terms of the electron density, ρ, and its Laplacian is quite similar to the nature of critical points observed in hydrogen bonds in the same systems. The ρ is inversely correlated to Cu-Cu distance. It is higher in asymmetrical systems than what is observed in corresponding symmetrical systems. By examining the ratio of the local electron potential-energy density (V(c)) to the kinetic energy density (G(c)), |V(c)|/G(c) at the critical point suggests that these interactions are not perfectly ionic but have some shared nature. Thus an analysis of critical points by using AIM theory points to the presence of an attractive metallophilic interaction similar to other well-documented weak interactions like hydrogen bonding.

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“…A positive ∇ 2 ρ indicates that kinetic electron energy density G(r) is greater than the potential electron energy density V(r). Such an interaction is observed in closed shell systems or a noncovalent interaction, where the depletion of electronic charge along the bond path is observed [37]. A negative value of ∇ 2 ρ at BCP indicates a covalent bond.…”

Section: Electron Density and Energy Decomposition Analysismentioning

confidence: 98%

Structure, electronic, inclusion complex formation behavior and spectral properties of pillarplex

Venkataramanan

Suvitha

2017

J Incl Phenom Macrocycl Chem

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systems. The low binding energy, and the physical adsorption of guest molecule and HOMO-LUMO spatial diagram indicates, that the Au and Ag-Pillarplex can be used as reversible host for linear alkanes Complexation of guest engenders frequency shift in the vibrational spectra. Calculated 1 H NMR reveal that guest protons which are closer to the metal sites experience larger shielding possibly due to C-H→LP* metal interaction. The 15 N signal observed for the DAO is nearly identical to that observed for the DAO@ metal-Pillarplex. NBO and AIM analysis indicate that metal centers in host, play a major role in stabilizing the guest inside the cavity than the amino group on the guest molecule.Abstract Electronic structure, vibrational and NMR spectra of metal-Pillarplex (metal = Cu, Ag and Au) and its inclusion complex with 1,8-diaminooctane (DAO) are investigated by using density functional theory. The coordinated metal atoms tune the cavity size and the height of metal-Pillarplex and form a rigid cavity thereby reducing their structural deformation. Cu-Pillarplex undergoes a large deformation both on the host and guest molecule. The calculated Gibbs free energy for the formation of inclusion complex were negative indicating their facile formation at the room temperature. Computed binding energies with various functionals and energy decomposition analysis, shows that dispersion correction is essential in these Electronic supplementary material The online version of this article (

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DFT studies and AIM analysis of intramolecular N–H···O hydrogen bonds in 3-aminomethylene-2 methoxy-5,6-dimethyl-2-oxo-2,3-dihydro-2λ5-[1,2]oxaphosphinin-4-one and its derivatives

Cited by 25 publications

References 56 publications

Co-crystal/salt crystal structure disorder of trichloroacetic acid–N-methylurea complex with double system of homo- and heteronuclear O–H···O/N–H···O hydrogen bonds: X-ray investigation, ab initio and DFT studies

Co-crystal/salt crystal structure disorder of trichloroacetic acid–N-methylurea complex with double system of homo- and heteronuclear O–H···O/N–H···O hydrogen bonds: X-ray investigation, ab initio and DFT studies

The Nature of Bond Critical Points in Dinuclear Copper(I) Complexes

Structure, electronic, inclusion complex formation behavior and spectral properties of pillarplex

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