Intramolecular exchange and "thermal" decoupling in B3H8-compounds

Beall, Herbert; Bushweller, C. Hackett; Dewkett, William J.; Grace, M. A.

doi:10.1021/ja00714a053

Cited by 58 publications

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“…The reactions of picoline-ligated hydridorhodathiaboranes (3-5) with C 2 H 4 and CO in this report resemble those found for the pyridine analog, 2, giving products of ligand substitution and cluster dehydrogenation (12)(13)(14)(15)(16)(17)(18)(19). These reactions nicely illustrate the structural flexibility and chemical tunability of these 11-vertex clusters and demonstre that the parent rhodathiaborane, [8, ) 2 -nido-8,7-RhSB 9 H 10 ] (1), first reported in 1990, 4 is actually a rich source of organometallic chemistry.…”

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confidence: 66%

“…In a similar fashion to the reactions with ethylene, the treatment of these pyridine and picolineligated hydridorhodathiaboranes, 2-5, with carbon monoxide affords the products of hydrogen loss and PPh 3 substitution, [1,1-(CO)(PPh 3 )-3-(L)-1,2-RhSB 9 H 8 ], (17)(18)(19) As we can see, thermal dehydrogenation, and reactions with CO and C 2 H 4 are convenient routes to the synthesis of 11-vertex rhodathiaboranes with closo / isonido-cluster geometries, which bear different exo-polyhedral ligands either at the metal centre or the boron-3 vertex. Thus, these reactions broaden the scope of the substitution chemistry in this system, allowing a systematic tuning of their reactivity.…”

Section: Studies Of Reactivitymentioning

confidence: 99%

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Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

et al. 2014

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The reaction between pyridine and [8, (17, 18, 19). These series of  2 -C 2 H 4 -and CO-ligated 11-vertex isonido / closorhodathiaboranes result from the substitution of one PPh 3 ligand by ethylene or CO together with H 2 loss and a concomitant nido-to-closo / isonido-cluster structural transformation. The reactivity of 3-5 with propene, 1-hexene and cyclohexene in a hydrogen atmosphere is also reported and compared with the reactivity of the pyridine-ligated analogue, [8,8,8-(H)(PPh 3 ) 2 -9-(NC 5 H 5 )-nido-8,7-RhSB 9 H 9 ] (2). Low temperature NMR studies have allowed the characterization of intermediates which undergo inter-and intramolecular exchange processes, depending on the nature of the N-heterocyclic ligand. The CO ligand enhances the non-rigidity of the cluster, opening mechanisms of H 2 loss from the clusters.) 3MANUSCRIPT TEXT

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confidence: 66%

Section: Studies Of Reactivitymentioning

confidence: 99%

Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

et al. 2014

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“…18 According to quantum‐chemical calculations,19 the C 2 v form is only slightly more stable than an alternative C s form. Indeed, [B 3 H 8 ] − was found to be highly fluxional in solution on the NMR time scale 20. Thus, at the borderline between classical organoboron and cluster chemistry, the molecular scaffold of [ 3 ] − resembles the transition‐state structure of the [B 3 H 8 ] − scrambling process.…”

Section: Methodsmentioning

confidence: 99%

Extensive Structural Rearrangements upon Reduction of 9H‐9‐Borafluorene

et al. 2014

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Common wisdom has it that organoboranes are readily oxidized. Described herein is that also their reduction can result in remarkable chemistry. Treatment of dimeric 9H-9-borafluorene with Li metal in toluene yields two strikingly different classes of compounds. One part of the sample reacts in a way similar to B2H6, thus affording an aryl(hydro)borane cluster reminiscent of the [B3H8](-) anion. The other part furnishes a dianionic boron-doped graphene flake devoid of hydrogen substituents at the boron centers and featuring a central B=B bond. A change in the solvent to THF allows an isolation of this dibenzo[g,p]chrysene analogue in good yields.

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“…Indeed, [B 3 H 8 ] À was found to be highly fluxional in solution on the NMR time scale. [20] Thus, at the borderline between classical organoboron and cluster chemistry, the molecular scaffold of [3] À resembles the transition-state structure of the [B 3 H 8 ] À scrambling process. In Scheme 1.…”

Section: Methodsmentioning

confidence: 99%

Extensive Structural Rearrangements upon Reduction of 9H‐9‐Borafluorene

Hübner¹,

Bolte²,

Lerner³

2014

Angewandte Chemie

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Common wisdom has it that organoboranes are readily oxidized. Described herein is that also their reduction can result in remarkable chemistry. Treatment of dimeric 9H-9borafluorene with Li metal in toluene yields two strikingly different classes of compounds. One part of the sample reacts in a way similar to B 2 H 6 , thus affording an aryl(hydro)borane cluster reminiscent of the [B 3 H 8 ] À anion. The other part furnishes a dianionic boron-doped graphene flake devoid of hydrogen substituents at the boron centers and featuring a central B=B bond. A change in the solvent to THF allows an isolation of this dibenzo [g,p]chrysene analogue in good yields.

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Intramolecular exchange and "thermal" decoupling in B3H8-compounds

Cited by 58 publications

References 1 publication

Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

Extensive Structural Rearrangements upon Reduction of 9H‐9‐Borafluorene

Extensive Structural Rearrangements upon Reduction of 9H‐9‐Borafluorene

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