Evidence for Higher Reactivity of B<sub>2</sub>. Theoretical Studies of Insertions of B<sub>2</sub> and B into Methane and Water

Wang, Zhixiang; Huang, Ming‐Bao

doi:10.1021/ja9807136

Cited by 21 publications

(22 citation statements)

References 28 publications

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“…Martin et al provided computational support for the experimental identification 14 of the borirene radical, BC 2 H 2 ; two other groups 15,16 elucidated the complicated mechanism for the reaction of B with C 2 H 2 . Our recent B3LYP DFT calculations found B 2 to be more reactive than a single boron atom with methane and water . The calculated activation energies for B insertion into methane and water differed significantly from those previously predicted at the semiempirical or lower ab initio levels …”

Section: Introductioncontrasting

confidence: 64%

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Theoretical Study of Boron−Ammonia Reactions

1999

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The mechanisms of the reactions of a boron atom (2P) and of B2 (3Σg -) with ammonia were studied computationally at the hybrid DFT B3LYP/6-311++G(3df, 2p)//B3LYP/6-311++G(2d,p) level. The B and B2 insertions into NH bonds take place by initial formation of BNH3 and BBNH3 complexes. As found previously for methane and water, B2 also is more reactive than B with ammonia. The energy-rich boron atom insertion product, HBNH2, then gives the species HBNH2, H2BNH, HBNH, and BNH. These can react with a second boron atom to give novel boron-containing compounds such as HBNBH, BNBH, H2BNBH, and BNB, some of which have been observed experimentally. However, contrary to the experimental suppositions, the only cyclic B2N minimum was a high-energy species.

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Section: Introductioncontrasting

confidence: 64%

“…The reactions of a boron atom with small molecules, such as CH 4 , − NH 3 , − H 2 O, ,− C 2 H 2 , − N 2 (N), − CO 2 , CO, , O 2 , and H 2 , have been investigated extensively. Many of the novel boron-containing products characterized computationally also have been observed experimentally.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of Boron−Ammonia Reactions

1999

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“…1 They have been the subject of numerous experimental [2][3][4][5][6][7][8][9] and theoretical [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] investigations. 1 They have been the subject of numerous experimental [2][3][4][5][6][7][8][9] and theoretical [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24]…”

Section: Introductionmentioning

confidence: 99%

Vibrations in the B4 rhombic structure

Linguerri

Navizet

Rosmus

et al. 2004

The Journal of Chemical Physics

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A double minimum six-dimensional potential energy surface (PES) is determined in symmetry coordinates for the most stable rhombic (D2h) B4 isomer in its 1Ag electronic ground state by fitting to energies calculated ab initio. The PES exhibits a barrier to the D4h square structure of 255 cm(-1). The vibrational levels (J=0) are calculated variationally using an approach which involves the Watson kinetic energy operator expressed in normal coordinates. The pattern of about 65 vibrational levels up to 1600 cm(-1) for all stable isotopomers is analyzed. Analogous to the inversion in ammonia-like molecules, the rhombus rearrangements lead to splittings of the vibrational levels. In B4 it is the B1g (D4h) mode which distorts the square molecule to its planar rhombic form. The anharmonic fundamental vibrational transitions of 11B4 are calculated to be (splittings in parentheses): G(0)=2352(22) cm(-1), nu1(A1g)=1136(24) cm(-1), nu2(B1g)=209(144) cm(-1), nu3(B2g)=1198(19) cm(-1), nu4(B2u)=271(24) cm(-1), and nu5(Eu)=1030(166) cm(-1) (D4h notation). Their variations in all stable isotopomers were investigated. Due to the presence of strong anharmonic resonances between the B1g in-plane distortion and the B2u out-of-plane bending modes, the higher overtones and combination levels are difficult to assign unequivocally.

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“…5 Following a series of significant experiments on isolated B n + (n = 2~17) 6,7 and B n (n = 2~52), 8 theoretical studies on bare boron clusters have strongly been stimulated. [9][10][11][12][13][14][15][16] Berkowitz and Chupka 17 were the first to study the mass spectra of B 2~5 clusters. Hanley et al 18 measured the appearance potentials and fragmentation patterns by studying the collision-induced dissociation of boron cluster ions containing up to 13 atoms.…”

Section: Introductionmentioning

confidence: 99%

Ab Initio Study on the Potential Energy Surfaces of B₄ Cluster

Jin

2003

J Chinese Chemical Soc

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The singlet and triplet potential energy surfaces (PES) for the isomerization and dissociation reactions of B4 isomers have been investigated using ab initio methods. Ten B4 isomers have been identified and of these 10 species, 4 have not been reported previously. The singlet rhombic structure 11 is found to be the most stable on the B4 surface, in agreement with the results of previous reports. Several isomerization and dissociation pathways have been found. On the singlet PES, the linear 13b can rearrange to rhombus 11 directly, while 13c rearranges to 11 through two‐step reactions involving a cyclic intermediate. On the triplet PES, the capped triangle structure 32 undergoes ring opening to the linear isomer 33b with a barrier of 34.8 kcal/mol and 44.9 kcal/mol, and the latter undergoes ring closure to the square structure 31 with a barrier of 30.4 kcal/mol and 33.0 kcal/mol at the MP4/6–311+G(3df)//MP2/6–311G(d) and CCSD/aug‐cc‐pVTZ//MP2/6–311G(d) levels of theory, respectively. The direct decomposition of singlet B4 yielding to B3+B is shown to have a large endothermicity of 87.3 kcal/mol (CCSD), and that producing 2B2 to have activation energy of 133.4 kcal/mol (CCSD).

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Evidence for Higher Reactivity of B₂. Theoretical Studies of Insertions of B₂ and B into Methane and Water

Cited by 21 publications

References 28 publications

Theoretical Study of Boron−Ammonia Reactions

Theoretical Study of Boron−Ammonia Reactions

Vibrations in the B4 rhombic structure

Ab Initio Study on the Potential Energy Surfaces of B₄ Cluster

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Evidence for Higher Reactivity of B2. Theoretical Studies of Insertions of B2 and B into Methane and Water

Cited by 21 publications

References 28 publications

Theoretical Study of Boron−Ammonia Reactions

Theoretical Study of Boron−Ammonia Reactions

Vibrations in the B4 rhombic structure

Ab Initio Study on the Potential Energy Surfaces of B4 Cluster

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Product

Resources

About

Evidence for Higher Reactivity of B₂. Theoretical Studies of Insertions of B₂ and B into Methane and Water

Ab Initio Study on the Potential Energy Surfaces of B₄ Cluster