Preparation and Structure of a New Boron Hydride, B20H16

Friedman, Lawrence B.; Dobrott, Robert D.; Lipscomb, William N.

doi:10.1021/ja00904a048

Cited by 44 publications

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“…HNO e H + + NOThis possibility should depend markedly on p H and the relative rates of reactions [6] and [4], with reaction [4] becoming more important in acid solution (1,3). When the p H is decreased from 7.1 (buffered solution) to 3.5, it is found that the transient still builds up in two distinct stages but the overall intensity decreases by about 75 %;…”

Section: T71mentioning

confidence: 99%

Pulse radiolysis of nitric oxide in aqueous solution

Seddon¹,

Young²

1970

Can. J. Chem.

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Pulse radiolysis of aqueous solutions of nitric oxide at neutral p H shows that the reaction initiated by the hydrated electron, e-(aq), proceeds via NO-and,a new transient thought to be (N,O,)-, and not HWO as indicated previously by steady state radiolysis.Canadian Journal of Chemistry, 48, 393 (1970) Earlier studies (1-31, on the radiation chemistry of nitric oxide solutions indicated that the products of y radiolysis, HNO, and N,O, were explicable by a fairly simple mecl-ranism(4 1 HNO i-%NO + tiNB2 t NiC While the above reaction sequence is stoichisnxtricaiiy correct the pulse radiolysis results demoi~strate that the detailed mechanism is more complex at neutral p%%, particularly with respect to reactions involvil~g anionic species generated via eV(aq).Figure 1 (open circ?esj, shows the trallsie~lt spectrum with absorption maxima at 250 and 380 my, observed from 1.7 mM NO solutio~~s 120 ps after a 2--3 krads, 0.5 ys pulse of electrons from a 2 MeV Van de GraafS accelerator. The spectrum 2 ys after the pulse appears identical and is about 20% lower in intensity at 380 mp. Addition of OH radical scavengers, 10-' M methanol or 2 x 10-% KRSCN, did not remove the transient. The absorption is not observed in 1.7 m M NO solutions containing 0.4 11.1 H2S04 as electron scavenger. Similarly, it is reduced by a factor of about 10 in solutions containing a 20-fold excess of N 2 0 , indicating that a precursor of this species is e-(aq).The permanent product absorption (closed circles) is due to the formation of nitrite (reaction [3]), which absorbs intensely at 210 mp (4). For personal use only.

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Section: T71mentioning

confidence: 99%

Pulse radiolysis of nitric oxide in aqueous solution

Seddon¹,

Young²

1970

Can. J. Chem.

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“…The synthesis of salts of the fac-[B 20 H 18 ] 2À ion would also seem to be possible starting from poorly accessible B 20 H 16 . [33,[35][36][37] The crystal structure of K 2 [B 20 H 18 ]·4 MeCN was determined, [38] and a view of the anion is shown in Figure 2. The anion consists of a nido-{B 11 } and a closo-{B 12 } fragment which share the B41, B42, and B43 atoms.…”

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closo‐[B₂₁H₁₈]⁻: A Face‐Fused Diicosahedral Borate Ion

et al. 2007

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“…A comparison of the experimentally determined and computationally calculated chemical shifts shown in Table I, suggests that the MP2(fc)/6-31G* geometry is a good representation of the actual geometry of B 20 H 16 in solution and, in turn, is in a good accord with the solid-state geometry reported in ref. 8 Despite being known for decades, little is understood of the chemistry of B 20 H 16 due to the difficulty of its synthesis. Essentially, the only aspect of its behaviour documented is the ready reactivity of B 20 H 16 toward Lewis bases,( e.g.…”

Section: Resultsmentioning

confidence: 99%

“…1, structure e) 7 , closo/closo B 20 H 16 (Fig. 1, structure d), respectively [8][9][10] . The latter of these compounds was first detected in the 1960's and experimentally shown to have a D 2d -symmetrical solid state structure (four kinds of boron atoms), whereas the former species was first synthesized and characterized only recently.…”

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confidence: 99%

“…The latter of these compounds was first detected in the 1960's and experimentally shown to have a D 2d -symmetrical solid state structure (four kinds of boron atoms), whereas the former species was first synthesized and characterized only recently. B 20 H 16 was prepared for the first time by slow passage of decaborane nido-B 10 H 14 vapour and H 2 through a discharge between Cu electrodes, and its solid-state structure determined by single-crystal X-ray diffraction 8 . Later an alternative synthetic route to B 20 H 16 was proposed based on the catalytic pyrolysis of decaborane at 350°C 9 .…”

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Revisiting B20H16 by means of a joint computational/experimental NMR approach

Hnyk

Holub

Jelı́nek

et al. 2010

Collect. Czech. Chem. Commun.

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Dedicated to Professor Bohumil Štíbr on the occasion of his 70th birthday as our gratitude to his achievements in boron cluster chemistry.A new synthesis of the fused macropolyhedral boron cluster B 20 H 16 is described and its molecular structure in solution discussed, based on multi-nuclear NMR spectra, including COSY measurements, in relation to its previously elucidated solid-state structure. To verify the conclusions from the NMR study, experimentally determined chemical shifts are compared with calculated values at the GIAO-B3LYP level with a TZP basis set by Huzinaga. There is a very good agreement between the experimental and computed δ( 11 B) values, suggesting that the MP2/6-31G* internal coordinates are a reasonable representation of the molecular geometry of this twenty-vertex cluster in solution that is essentially the same as its solid-state structure. A computational analysis of the FMO orbitals of B 20 H 16 , in particular of the LUMO, reveals that the four naked boron atoms, common for two shared icosahedral subclusters, are the reactive sites of this D 2d -symmetrical molecule.The icosahedron is the most symmetrical way to arrange twelve atoms into a polyhedral cluster and is the quintessential structural motif in boron hydride cluster chemistry, classically represented by the [closo-B 12 H 12 ] 2-dianion (Fig. 1, structure a). This dianion belongs to a point group of I h symmetry and is considered to be a three-dimensional aromatic system 1 . Such structural architectures are also found in elemental boron itself. Replacement of individual {BH} 2-vertices in this twelve-vertex polyhedral cluster by various isoelectronic and isolobal 2 main-group element units

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Preparation and Structure of a New Boron Hydride, B₂₀H₁₆

Cited by 44 publications

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Pulse radiolysis of nitric oxide in aqueous solution

Pulse radiolysis of nitric oxide in aqueous solution

closo‐[B₂₁H₁₈]⁻: A Face‐Fused Diicosahedral Borate Ion

Revisiting B20H16 by means of a joint computational/experimental NMR approach

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Preparation and Structure of a New Boron Hydride, B20H16

Cited by 44 publications

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Pulse radiolysis of nitric oxide in aqueous solution

Pulse radiolysis of nitric oxide in aqueous solution

closo‐[B21H18]−: A Face‐Fused Diicosahedral Borate Ion

Revisiting B20H16 by means of a joint computational/experimental NMR approach

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Preparation and Structure of a New Boron Hydride, B₂₀H₁₆

closo‐[B₂₁H₁₈]⁻: A Face‐Fused Diicosahedral Borate Ion