Synthesis of the new boron hydride nido-undecaborane(15), B11H15, and the x-ray structure of its conjugate base tetradecahydroundecaborate(1-), [B11H14]-

Getman, Thomas D.; Krause, Jeanette A.; Shore, Sheldon G.

doi:10.1021/ic00287a006

Cited by 37 publications

(31 citation statements)

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“…The bond parameters of the B−C≡N units of 5 a and 6 a are similar to those of the closo clusters of 2 and 3 (Table ). The intracluster B−B distances of 5 a and 6 a are similar, too, and they are similar to d (B−B) reported earlier for related { nido ‐B 11 } cages: [ nido ‐B 11 H 13 ] 2− ( 4 a ), [7‐R‐ nido ‐B 11 H 13 ] − (R=H ( 4 b ), OEt, 1,1,2‐trimethylpropyl), 7‐Me 2 S‐ nido ‐B 11 H 13 , and [7‐C 5 H 5 N‐ nido ‐B 11 H 12 ] − …”

Section: Resultssupporting

confidence: 87%

Stepwise Introduction of Cyano Groups into nido‐ and closo‐Undecaborate Clusters

Konieczka

Schlüter

Sindorf

et al. 2018

Chemistry A European J

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Eleven-vertex closo and nido boron clusters with one or two exo-cyano groups were obtained by a series of consecutive cage-opening and cage-closure reactions starting from K [closo-B H ] (K 1). In the first step, K 1 reacts with KCN in water at elevated temperatures to yield [7-NC-nido-B H ] (5 a). Oxidation of 5 a with PbO gives [NC-closo-B H ] (2). In analogous subsequent reactions, dianion 2 was converted with KCN regioselectively to [7,9-(NC) -nido-B H ] (6 a), which was further oxidized to [(NC) -closo-B H ] (3). The {nido-B } dianions 5 a and 6 a were protonated to yield [7-NC-nido-B H ] (5 b) and [7,9-(NC) -nido-B H ] (6 b). All anions were studied by NMR spectroscopy and, except for 6 b, salts of all anions were characterized by IR and Raman spectroscopy and by elemental analysis. The position of the cyano group(s) in 5 a and 6 a were confirmed by NMR data and single-crystal X-ray diffraction studies on [Ph P] 5 a⋅CH Cl and [Et N] 6 a. The {closo-B } clusters are fluxional in solution. In the crystal of [EMIm] 2 the BCN vertex is in the 2-position. Two isomers of dianion 3, [2,3-(NC) -closo-B H ] and [2,6-(NC) -closo-B H ] , were identified in the crystal of its [Et N] salt. The peak oxidation potentials E of anions 1-3, 5 a, 6 a, 5 b, and [nido-B H ] (4 b), determined by cyclic voltammetry, increase with increasing number of cyano groups. Increasing E in the order 1<2<3 parallels the increasing reactivity toward cyanide anions.

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Section: Resultssupporting

confidence: 87%

Stepwise Introduction of Cyano Groups into nido‐ and closo‐Undecaborate Clusters

Konieczka

Schlüter

Sindorf

et al. 2018

Chemistry A European J

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“…This structure has been confirmed for the first three in the series by NMR and for the mono-and dianion also by X-ray structural analysis [1,2]. All of these three clusters exhibit C 5v symmetry in solution because of the mobility of the extra H atoms at the pentagonal aperture; these H atoms were shown to jump from bridging into endo-positions and vice versa and this process is rapid with respect to the NMR time scale [3].…”

Section: Introductionmentioning

confidence: 54%

“…All of these three clusters exhibit C 5v symmetry in solution because of the mobility of the extra H atoms at the pentagonal aperture; these H atoms were shown to jump from bridging into endo-positions and vice versa and this process is rapid with respect to the NMR time scale [3]. The easiest synthetic approach to the series is the reaction of NaBH 4 with BF 3 (OEt 2 ) in diglyme at 105°C, yielding [B 11 H 14 ] ± [4], which can subsequently be protonated [1] or deprotonated [5] 12 ] 3± has been described in a dissertation, but no pure product had been isolated [6]. The tetraanion [B 11 [11], two minima could be detected on the potential energy hyperface.…”

Section: Introductionmentioning

confidence: 99%

“…In order to test our calculation, we also computed the geometries of [B 11 H 13 ] 2± and [B 11 H 14 ] ± , starting from the known structures of these anions in the crystal [1,2], optimized the geometries and used them for a GIAO calculation of the 11 B NMR data, applying again the HF and the B3LYP/6±31G(d,p) levels. There is again sufficient correspondence of the experimental and calculated 11 B NMR data ( Table 1; the observed values refer to our own measurement in [D 8 ]thf).…”

Section: Introductionmentioning

confidence: 99%

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Dodecahydro-nido-undecaborate [B11H12]3-

Dirk

Paetzold

Radacki

2001

Z. anorg. allg. Chem.

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The deprotonation of the nido-anion [B 11 H 14 ] ± by two equivalents of LitBu yields the anion [B 11 H 12 ] 3± . Three observed 11 B NMR shifts of this anion in the ratio 1 : 5 : 5 are in agreement with shifts calculated by the GIAO method on the basis of the ab initio computed geometry. The deprotonation can be reversed, giving back [B 11 H 14 ] ± via [B 11 H 13 ] 2± . The thermolysis of [Li(thp) x ] 3 [B 11 H 12 ] in thp at 80°C leads to the closo-borate [Li(thp) 3 ] 2 [B 11 H 11 ] under elimination of LiH. Anhydrous air transforms [B 11 H 12 ] 3± into the known oxa-nido-dodecaborate [OB 11 H 12 ] ± . The rhoda-closo-dodecaborate [L 2 RhB 11 H 11 ] 3± is formed from [B 11 H 12 ] 3± and RhL 3 Cl (L = PPh 3 ). Dodecahydro-nido-undecaborat [B 11 H 12 ] 3± Inhaltsu È bersicht. Das nido-Anion [B 11 H 14 ] ± la È ût sich mit zwei Øquivalenten LitBu zum Anion [B 11 H 12 ] 3± deprotonieren. Drei 11 B-NMR-Verschiebungen im Verha È ltnis 1 : 5 : 5 stimmen mit Verschiebungen u È berein, die mit der GIAOMethode auf der Grundlage der ab initio ermittelten Geometrie berechnet wurden. Protoniert man umgekehrt [B 11 H 12 ] ± , so gelangt man u È ber [B 11 H 13 ] 2± zu [B 11 H 14 ] ± zuru È ck. Die Thermolyse von [Li(thp) x ] 3 [B 11 H 12 ] in thp bei 80°C fu È hrt unter Abspaltung von LiH zum closo-Borat [Li(thp) 3 ] 2 [B 11 H 11 ]. Wasserfreie Luft oxidiert [B 11 H 12 ] 3± zum bekannten Oxa-nido-dodecaborat [OB 11 H 12 ] ± . Aus [B 11 H 12 ] 2± und RhL 3 Cl bildet sich das Rhoda-closo-dodecaborat [L 2 RhB 11 H 11 ] 3± (L = PPh 3 ).

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“…Undecaborane (15), B 11 H 15 [21], is the largest among experimentally known homonuclear nido-boranes with a Wade type cluster. On the other hand, the smallest macropolyhedra is nido (6)-[2]-nido(8)-B 12 H 16 [12].…”

Section: For Which Cluster Sizes Are Macropolyhedral Structures To Bementioning

confidence: 99%

Rules for macropolyhedral boranes

Hofmann¹,

Kiani²

2009

Journal of Organometallic Chemistry

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Synthesis of the new boron hydride nido-undecaborane(15), B11H15, and the x-ray structure of its conjugate base tetradecahydroundecaborate(1-), [B11H14]-

Cited by 37 publications

References 0 publications

Stepwise Introduction of Cyano Groups into nido‐ and closo‐Undecaborate Clusters

Stepwise Introduction of Cyano Groups into nido‐ and closo‐Undecaborate Clusters

Dodecahydro-nido-undecaborate [B11H12]3-

Rules for macropolyhedral boranes

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