Some measures for mediating the strengths of halogen bonds with the B-B bond in diborane(4) as an unconventional halogen acceptor

Zhuo, Hongying; Yu, Hong; Li, Wenzuo; Cheng, Jianbo

doi:10.1002/qua.24533

Cited by 10 publications

(8 citation statements)

References 64 publications

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“…The halogen bond has been computationally characterized by the interaction of a region of positive electrostatic potential on the halogen atoms, known as the σ-hole, with the negative electrostatic potential of a Lewis base [13][14][15][16]. A large number of different Lewis bases have been used to form such complexes [11], including carbenes [17,18], boron derivatives [19][20][21][22], σ-bonds [23,24] and π-systems [25,26]. As with the hydrogen bond, the effects of cooperativity [27,28] in the clusters formed by halogen bonds or in connection with other noncovalent bonds have been observed [29][30][31][32][33].…”

Section: Introductionmentioning

confidence: 99%

Hydrogen vs. Halogen Bonds in 1-Halo-Closo-Carboranes

2020

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A theoretical study of the hydrogen bond (HB) and halogen bond (XB) complexes between 1-halo-closo-carboranes and hydrogen cyanide (NCH) as HB and XB probe has been carried out at the MP2 computational level. The energy results show that the HB complexes are more stable than the XBs for the same system, with the exception of the isoenergetic iodine derivatives. The analysis of the electron density with the quantum theory of atoms in molecules (QTAIM) shows the presence of a unique intermolecular bond critical point with the typical features of weak noncovalent interactions (small values of the electron density and positive Laplacian and total energy density). The natural energy decomposition analysis (NEDA) of the complexes shows that the HB and XB complexes are dominated by the charge-transfer and polarization terms, respectively. The work has been complemented with a search in the CSD database of analogous complexes and the comparison of the results, with those of the 1-halobenzene:NCH complexes showing smaller binding energies and larger intermolecular distances as compared to the 1-halo-closo-carboranes:NCH complexes.

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Section: Introductionmentioning

confidence: 99%

Hydrogen vs. Halogen Bonds in 1-Halo-Closo-Carboranes

2020

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“…In 2011, we demonstrated that diborane (4) (B 2 H 4 ) could behave as an electron donor to form a hydrogen bond through its B−B covalent bond. Others have considered B as an electron donor to form a halogen bond . In 1998, two groups independently isolated the first borylene complexes of transition metals .…”

Section: Introductionmentioning

confidence: 99%

“…Others have considered Ba sa ne lectron donor to form ah alogen bond. [7] In 1998, two groups independently isolated the first borylene complexeso ft ransition metals. [8,9] A2 000 review summarized the experimental and theoretical studies of borylene ligands in transition-metal chemistry.…”

Section: Introductionmentioning

confidence: 99%

Boron as an Electron‐Pair Donor for B⋅⋅⋅Cl Halogen Bonds

2016

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MP2/aug'-cc-pVTZ calculations were performed to investigate boron as an electron-pair donor in halogen-bonded complexes (CO) (HB):ClX and (N ) (HB):ClX, for X=F, Cl, OH, NC, CN, CCH, CH , and H. Equilibrium halogen-bonded complexes with boron as the electron-pair donor are found on all of the potential surfaces, except for (CO) (HB):ClCH and (N ) (HB):ClF. The majority of these complexes are stabilized by traditional halogen bonds, except for (CO) (HB):ClF, (CO) (HB):ClCl, (N ) (HB):ClCl, and (N ) (HB):ClOH, which are stabilized by chlorine-shared halogen bonds. These complexes have increased binding energies and shorter B-Cl distances. Charge transfer stabilizes all complexes and occurs from the B lone pair to the σ* Cl-A orbital of ClX, in which A is the atom of X directly bonded to Cl. A second reduced charge-transfer interaction occurs in (CO) (HB):ClX complexes from the Cl lone pair to the π* C≡O orbitals. Equation-of-motion coupled cluster singles and doubles (EOM-CCSD) spin-spin coupling constants, J(B-Cl), across the halogen bonds are also indicative of the changing nature of this bond. J(B-Cl) values for both series of complexes are positive at long distances, increase as the distance decreases, and then decrease as the halogen bonds change from traditional to chlorine-shared bonds, and begin to approach the values for the covalent bonds in the corresponding ions [(CO) (HB)-Cl] and [(N ) (HB)-Cl] . Changes in B chemical shieldings upon complexation correlate with changes in the charges on B.

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“…To have a further insight into the halogen bonding, the changes in electron density that arises during the formation of the complexes were analysed. Total electron density maps have been shown to accurately determine electron density shifts [36]. The electron density shifts that occur in tetrahydro-1,3-oxazine:BrF complexes are shown in Fig.…”

Section: Noncovalent Interactions (Nci) Index Of the Halogen Bondmentioning

confidence: 98%

Revealing halogen bonding interactions with anomeric systems: An ab initio quantum chemical studies

Ganguly

2015

Journal of Molecular Graphics and Modelling

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Some measures for mediating the strengths of halogen bonds with the B-B bond in diborane(4) as an unconventional halogen acceptor

Cited by 10 publications

References 64 publications

Hydrogen vs. Halogen Bonds in 1-Halo-Closo-Carboranes

Hydrogen vs. Halogen Bonds in 1-Halo-Closo-Carboranes

Boron as an Electron‐Pair Donor for B⋅⋅⋅Cl Halogen Bonds

Revealing halogen bonding interactions with anomeric systems: An ab initio quantum chemical studies

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