Dodecahydro-nido-undecaborate [B11H12]3-

Dirk, W.; Paetzold, Peter; Radacki, Krzysztof

doi:10.1002/1521-3749(200112)627:12<2615::aid-zaac2615>3.0.co;2-m

Cited by 12 publications

(8 citation statements)

References 6 publications

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“…The reaction of dianions 1 and 2 with CN − to yield 6 a hints at a great potential of related cluster‐opening reactions induced by strong nucleophiles. Furthermore, salts of the nido clusters 5 a and 6 a are promising starting materials for, for example, cluster Aufbau and related reactions, similar to transformations with salts of the parent nido cage [ nido ‐B 11 H 14 ] − …”

Section: Resultsmentioning

confidence: 99%

“…They act as weakly coordinating anions or as ligands, for example, in [Ag 7 (12‐C≡C‐ closo ‐1‐CB 11 H 11 ) 4 (3,5‐Me 2 Py) 10 ] − . Aufbau reactions with transition metal (M) fragments to give { closo ‐MB 11 } clusters have been described as well . Further important reactions of the [ nido ‐B 11 H 14 ] − anion are oxidations to decaborane(14) ( nido ‐B 10 H 14 ), [ nido ‐OB 11 H 12 ] − , or [ closo ‐B 11 H 11 ] 2− (Scheme ) .…”

Section: Introductionmentioning

confidence: 99%

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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: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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“…However, an artificial molecule, BC (Table A, Supporting Information), with the HH structural feature, and with fixed hydrogen boron distances, was 9.4 kcal mol -1 higher in energy than BA . For [B 11 H 12 ] 3- , the transition state CB is 4.9 kcal mol -1 higher in energy than CA (see Figure ).…”

Section: Resultsmentioning

confidence: 99%

“… a In the case of more than one reference, the compound was first reported in the first reference; for example, synthesis of B 11 H 13 2- ( BA ) was first reported in 1988 (ref ) and again in 2001 (ref ). b Molecular structure determination by gas-phase electron diffraction.…”

Section: Introductionmentioning

confidence: 99%

Structural Increment System for 11-Vertexnido-Boranes and Carboranes

Kiani

Hofmann

2004

Inorg. Chem.

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An increment system forming a set of quantitative rules that govern the relative stabilities of 11-vertex nido-boranes and carboranes is presented. Density functional theory computations at the B3LYP/6-311+G//B3LYP/6-31G level with ZPE corrections were carried out for 61 different boron hydride and carborane structures from [B(11)H(14)](-) to C(4)B(7)H(11) to determine their relative stabilities. Disfavored structural features that destabilize a cluster structure relative to a hypothetical ideal situation were identified and weighted by so-called energy penalties. The latter show additive behavior and allow us to reproduce (within 5 kcal mol(-)(1)) the DFT computed relative energies. Energy penalties for four structural features, i.e., adjacent carbon atoms, CC, a hydrogen atom bridging between a carbon and a boron atom, CH-B, an endo-terminal hydrogen atom at an open face carbon atom, CH(2) and an endo-H between two carbon atoms, C(BH(2))C for the 11-vertex nido-cluster are quite similar to those reported for the 6-vertex nido-cluster, thus showing a behavior independent of the cluster size. Hydrogen structural features, however, vary strongly with the cluster size. Two unknown 11-vertex nido-carboranes were identified which are thermodynamically more stable than known positional isomers.

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“…Isomers EB through ED are at least 25 kcal mol À1 less stable than EA. A similar profound preference is found for the heteroatom apart nido-7,9-isomer (FA) [70] among [SCB 9 H 10 ] À structures. The experimentally known nido-7,9,10-SC 2 B 8 H 10 (GA) [3] is the most stable of the seven computed isomers.…”

Section: Thia(carba)boranes and -Boratesmentioning

confidence: 94%

Periodic trends and easy estimation of relative stabilities in 11-vertex nido-p-block-heteroboranes and -borates

Kiani¹,

Hofmann²

Highlights in Computational Chemistry II

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Density functional theory computations were carried out for 11-vertex nido-p-block-hetero(carba)boranes and -borates containing silicon, germanium, tin, arsenic, antimony, sulfur, selenium and tellurium heteroatoms. A set of quantitative values called ''estimated energy penalties'' was derived by comparing the energies of two reference structures that differ with respect to one structural feature only. These energy penalties behave additively, i.e., they allow us to reproduce the DFT-computed relative stabilities of 11-vertex nidoheteroboranes in general with good accuracy and to predict the thermodynamic stabilities of unknown structures easily. Energy penalties for neighboring heteroatoms (HetHet and HetHet¢) decrease down the group and increase along the period (indirectly proportional to covalent radii). Energy penalties for a fiverather than four-coordinate heteroatom, [Het 5k (1) and Het 5k (2)], generally, increase down group 14 but decrease down group 16, while there are mixed trends for group 15 heteroatoms. The sum of HetHet¢ energy penalties results in different but easily predictable openface heteroatom positions in the thermodynamically most stable mixed heterocarbaboranes and -borates with more than two heteroatoms.

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Dodecahydro-nido-undecaborate [B11H12]3-

Cited by 12 publications

References 6 publications

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

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

Structural Increment System for 11-Vertexnido-Boranes and Carboranes

Periodic trends and easy estimation of relative stabilities in 11-vertex nido-p-block-heteroboranes and -borates

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