Identification of diborane(4) with bridging B–H–B bonds

Chou, Sheng‐Lung; Lo, Jen‐Iu; Peng, Yu‐Chain; Lin, Meng‐Yeh; Lu, Hsiao‐Chi; Cheng, Bing‐Ming; Ogilvie, J. F.

doi:10.1039/c5sc02586a

Cited by 38 publications

(42 citation statements)

References 42 publications

(63 reference statements)

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“…According to Greenwood and Earnshaw, “Boron is a unique and exciting element… like C and Si, it shows a marked propensity to form covalent molecular compounds, but it differs sharply from them in having one less valence electron than the number of valence orbitals, a situation sometimes referred to as electron deficiency.” In view of its electron deficiency, boron has long been regarded as an electron‐acceptor atom. However, beginning in 1999, a few papers raised the possibility that boron may act as an electron‐pair donor . 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.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Introductionmentioning

confidence: 99%

“…However,beginningi n1999, af ew papers raised the possibility that boron may act as an electron-pair donor. [2][3][4][5][6] In 2011, we demonstrated that diborane(4) (B 2 H 4 )c ould behave as an electron donor to form ah ydrogen bond through its BÀBc ovalent bond. Others have considered Ba sa ne lectron donor to form ah alogen bond.…”

Section: Introductionmentioning

confidence: 99%

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

2016

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“…Hence, no neutral species has been identified experimentally until 2015, when Chou irradiated diborane (6) dispersed in neon at 3 K with far-ultraviolet light, detecting diborane(4), B 2 H 4 (Figure 1b). 40 This new species with two terminal hydrogen atoms possesses two bridging hydrogen atoms, and so it became the simplest neutral boron hydride identified with such a structural feature. (4).…”

Section: Diboranesmentioning

confidence: 99%

“…In the present article, we apply this theory to systems with electron-deficient bonds, i.e., to compounds which have too few valence electrons for the connections between atoms to be described as covalent bonds, and which have always fascinated chemists. First we apply the theory to the notoriously known textbook example of the diborane(6) 39 molecule (B 2 H 6 ) with two-electron threecenter bridge bonds and then also to recently characterized diborane(4) 40 (B 2 H 4 ) and zero-valent complexes of beryllium 41,42 . The neutral form of the latter compound exhibits surprising stability, which was attributed to a strong three-center two-electron π bond stretching across the C-Be-C core 41 .…”

Section: Introductionmentioning

confidence: 99%

Quantum information-based analysis of electron-deficient bonds

Brandejs

Veis

Szalay

et al. 2019

The Journal of Chemical Physics

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Recently, the correlation theory of the chemical bond was developed, which applies concepts of quantum information theory for the characterization of chemical bonds, based on the multiorbital correlations within the molecule. Here for the first time, we extend the use of this mathematical toolbox for the description of electron-deficient bonds. We start by verifying the theory on the textbook example of a molecule with three-center two-electron bonds, namely the diborane(6). We then show that the correlation theory of the chemical bond is able to properly describe bonding situation in more exotic molecules which have been synthetized and characterized only recently, in particular the diborane molecule with four hydrogen atoms [diborane(4)] and neutral zerovalent s-block beryllium complex, whose surprising stability was attributed to a strong three-center twoelectron π bond stretching across the C-Be-C core. Our approach is of a high importance especially in the light of a constant chase after novel compounds with extraordinary properties where the bonding is expected to be unusual.

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“…The structure of B 2 H 6 involves bridging and contains two three‐centered bonds (as presented in Figure ). There are two stable isotopic variants of diborane: 80% and 20% for 11 B and 10 B, respectively . The most abundant species of diborane is 11 B 2 H 6 .…”

Section: Introductionmentioning

confidence: 99%

Nuclear quantum and H/D isotope effects on three‐centered bonding diborane: Path integral molecular dynamics simulations

Daengngern

Kobayashi

Kungwan

et al. 2020

Int J of Quantum Chemistry

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Nuclear quantum and H/D isotope effects of bridging and terminal hydrogen atoms of diborane (B2H6) molecules were systematically studied by classical ab initio molecular dynamics (CLMD) and ab initio path integral molecular dynamics (PIMD) simulations with BHandHLYP/6‐31++G** level of theory at room temperature (298.15 K). Calculated results clearly show that H/D isotope effect appears in the distribution of hydrogen (deuterium) of B2H6 (B2D6). Geometry of B2H6 also plays a significant role in the nuclear quantum effect proved by PIMD simulations, but slightly deviated from its equilibrium structure when simulated via CLMD simulation. The bond lengths between boron atoms R (B1 … B2) and the bridging hydrogen atoms RHH (HB1 … HB2) of the B2H6 molecule obtained from PIMD simulations are slightly longer than those of the deuterated form of the diborane (B2D6) molecule. The principal component analysis (PCA) was also employed to distinguish the important modes of bridging hydrogen as related to the nuclear quantum and H/D isotope effects. The highest level of contribution obtained from PCA of PIMD simulations is bending, while various mixed vibrations with less contribution were also found. Therefore, the nuclear quantum and H/D isotope effects need to be taken into account for a better understanding of diborane geometry.

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Identification of diborane(4) with bridging B–H–B bonds

Abstract: The irradiation of diborane(6) dispersed in solid neon at 3 K with far-ultraviolet light generated diborane(4), B2H4, with bridging B–H–B bonds.

Cited by 38 publications

References 42 publications

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

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

Quantum information-based analysis of electron-deficient bonds

Nuclear quantum and H/D isotope effects on three‐centered bonding diborane: Path integral molecular dynamics simulations

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