Theoretical studies of conformational analysis and intramolecular dynamic phenomena

Alkorta, Ibón; Elguero, José

doi:10.1007/s11224-019-01370-5

Cited by 6 publications

(6 citation statements)

References 191 publications

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“…The excellent exponential correlation between ρ BCP and the P−C distance has a correlation coefficient of 0.998 and can be seen in Figure S3 a. These data are in agreement with data reported previously for hydrogen bonds and other weak interactions …”

Section: Resultssupporting

confidence: 91%

Carbenes as Electron‐Pair Donors for P⋅⋅⋅C Pnicogen Bonds

2017

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Ab initio MP2/aug'-cc-pVTZ calculations were performed on the P⋅⋅⋅C pnicogen-bonded complexes of the singlet carbene molecules C(NH ) , C(OH) , and cyclic C(OCH) [OHC] with H XP molecules, with X=F, Cl, NC, OH, CH , CN, CCH, and H. The H XP:C(NH ) and H XP:C(OH) complexes have C symmetry and two different structures: one in which the symmetry plane of the complex and the local symmetry plane of the carbene are non-coplanar, and the other in which they are coplanar. The non-coplanar H XP:C(NH ) and H XP:C(OH) complexes arise only when X is one of the more electronegative substituents. Coplanar H XP:C(NH ) complexes form when X is one of the more electropositive substituents, whereas coplanar H XP:C(OH) complexes exist for all X. H XP:C(NH ) and H XP:C(OH) are stabilized by covalent P-C bonds or P⋅⋅⋅C pnicogen bonds, but co-planar H (CH )P:C(OH) and H P:C(OH) are stabilized by O-H⋅⋅⋅P hydrogen bonds. The H XP:OHC complexes have non-coplanar structures that are also stabilized by P-C covalent bonds or pnicogen bonds. The H (CH )P:OHC and H P:OHC complexes in which the symmetry plane of the complex and the local symmetry plane of the carbene are perpendicular are stabilized by P⋅⋅⋅π bonds with P acting as the electron-pair donor to the OHC π system. The H XP:C(NH ) , H XP:C(OH) , and H XP:OHC complexes are described in terms of their binding energies, charge-transfer energies, electron density properties, and equation-of-motion coupled cluster singles and doubles spin-spin coupling constants.

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Section: Resultssupporting

confidence: 91%

Carbenes as Electron‐Pair Donors for P⋅⋅⋅C Pnicogen Bonds

2017

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“…As the J ( 209 Bi– 31 P) coupling constants in 2 a – c are ruled by the Fermi contact term and the PSO and SD contributions are insignificant, this coupling mechanism is through‐space in nature, in accord with the Mallory‐type lone pair overlap theory reported for 19 F– 19 F, 19 F– 15 N and 31 P– 31 P through‐space couplings . The s‐character of the P and Bi lone pairs in compounds 2 a – c is very similar (approximately P: 55 %, Bi: 97 %), however, the overlap of the two lone pairs depends on the distance between the two atoms, which is clearly determined by the strength of the pnictogen interaction …”

Section: Methodsmentioning

confidence: 95%

Weak Pnictogen Bond with Bismuth: Experimental Evidence Based on Bi−P Through‐Space Coupling

Mokrai

Barrett

Apperley

et al. 2019

Chemistry A European J

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To study pnictogen bonding involving bismuth, flexible accordion‐like molecular complexes of the composition [P(C 6 H 4 ‐ o ‐CH 2 SCH 3 ) 3 BiX 3 ], (X=Cl, Br, I) have been synthesised and characterised. The strength of the weak and mainly electrostatic interaction between the Bi and P centres strongly depends on the character of the halogen substituent on bismuth, which is confirmed by single‐crystal X‐ray diffraction analyses, DFT and ab initio computations. Significantly, 209 Bi– 31 P through‐space coupling ( J =2560 Hz) is observed in solid‐state 31 P NMR spectra, which is so far unprecedented in the literature, delivering direct information on the magnitude of this pnictogen interaction.

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“…They are potential nucleophiles for the capture, activation, and transformation of CO 2 . [ 8–10 ] Their carbenic carbon may exist in a singlet state or appear in two symmetry‐distinct triplet states with a similar energy [ 11,12 ] (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Capture of CO₂ by novel diiodo‐N,N‐imidazoliumvinylidene: A theoretical quest

Soroudi

Kassaee

2022

J of Physical Organic Chem

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Capture of CO 2 by diiodo-N,N-imidazoliumvinylidene, with singlet and triplet minima (1 s and 1 t , respectively), is probed at M06-2X/6-311++G ** level of theory. Ground state appears to be triplet 1 t , which exhibits a rather large singlettriplet energy gap (ΔE s-t = +10.30 kcal mol À1 ). Adsorption of CO 2 over 1 t releases À3.70 kcal mol À1 energy and gives the initial CO 2 adduct, with no transition state (TS). Sequentially, the latter goes through a reactant-like TS, which leads to an internal exothermic attack of the carbene carbon to the adsorbed CO 2 and forms 3 t with conversion energy (E con ) of À6.77 kcal mol À1 . Additional calculations involve endothermic capture of CO 2 by the rather unstable 1 s . The immense potential of the natural bond orbital (NBO) and atom in molecule (AIM) data in elucidating a reaction mechanism is unveiled by employing the electron-pushing technique. Results appear consistent with the proposed mechanism.

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Theoretical studies of conformational analysis and intramolecular dynamic phenomena

Cited by 6 publications

References 191 publications

Carbenes as Electron‐Pair Donors for P⋅⋅⋅C Pnicogen Bonds

Carbenes as Electron‐Pair Donors for P⋅⋅⋅C Pnicogen Bonds

Weak Pnictogen Bond with Bismuth: Experimental Evidence Based on Bi−P Through‐Space Coupling

Capture of CO₂ by novel diiodo‐N,N‐imidazoliumvinylidene: A theoretical quest

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Theoretical studies of conformational analysis and intramolecular dynamic phenomena

Cited by 6 publications

References 191 publications

Carbenes as Electron‐Pair Donors for P⋅⋅⋅C Pnicogen Bonds

Carbenes as Electron‐Pair Donors for P⋅⋅⋅C Pnicogen Bonds

Weak Pnictogen Bond with Bismuth: Experimental Evidence Based on Bi−P Through‐Space Coupling

Capture of CO2 by novel diiodo‐N,N‐imidazoliumvinylidene: A theoretical quest

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Capture of CO₂ by novel diiodo‐N,N‐imidazoliumvinylidene: A theoretical quest