Structural chemistry of halogenated monocarbaboranes: the extended structures of Cs[1-HCB9H4Br5], Cs[1-HCB11H5Cl6] and Cs[1-HCB11H5Br6]

Franken, Andreas; Bullen, Neil J.; Jelı́nek, Tomáš; Thornton‐Pett, Mark; Teat, Simon J.; Clegg, William; Kennedy, John D.; Hardie, Michaele J.

doi:10.1039/b410929e

Cited by 42 publications

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“…[31] NMR spectra: The three anionic gold(I) carba-closo-borate complexes 1, 2, and 3 were characterized by 1 H signals were assigned with the aid of 11 B{ 1 H}-1 HA C H T U N G T R E N N U N G { 11 B} correlation experiments (see the Experimental Section). [48] The 13 C chemical shifts of the cluster carbon atoms in the gold(I) complexes 1-3 are shifted to higher resonance frequencies than the parent anions [closo-1-CB 11 H 12 ] À , [1,49] [closo-1-CB 9 H 10 ] À , [18] and [closo-2-CB 9 H 10 ] À , [18] respectively (Table 5). For the phenyl-substituted anions, 13 C NMR À anion in the crystal structure of [Et 4 N]-3.…”

Section: N]mentioning

confidence: 95%

“…[18,19] In contrast to monocarba-closo-borates, the coordination chemistry of dicarba-closo-dodecaboranes and dicarbacloso-decaboranes with 2c-2e s bonds between one or both cluster carbon atoms and metal centers is well established. [20] Some linear gold(I) complexes with 1,2-1,7-, and 1,12-dicarba-closo-dodecaboranes with tertiary phosphane and arsane ligands have been reported [21] and synthetic, spectroscopic, and structural properties are available for most of these coordination compounds.…”

Section: àmentioning

confidence: 99%

“…Similar preparations of other derivatives of the {closo-1-CB 9 } cluster have been described in the literature, [17-19, 30, 31] for example, the isomerization of Cs[closo-2-CB 9 H 10 ] to Cs[closo-1-CB 9 H 10 ]. [18] The ) can be given because the isomerization peak is partially covered by a second peak that is assigned to a phase transition.…”

Section: àmentioning

confidence: 99%

“…[7,53] . [18] Thermal isomerization of Cs[closo-2-CB 9 H 10 ] resulted in Cs[closo-1-CB 9 H 10 ]. [18,55] Decaborane (14) À (3), and related carba-closo-borate anions.…”

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confidence: 99%

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Anionic Gold(I) Complexes—Twelve‐ and Ten‐Vertex Monocarba‐closo‐borate Anions with Carbon–Gold σ Bonds

Finze

Sprenger

2009

Chemistry A European J

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The anionic gold(I) complexes [1-(Ph(3)PAu)-closo-1-CB(11)H(11)](-) (1), [1-(Ph(3)PAu)-closo-1-CB(9)H(9)](-) (2), and [2-(Ph(3)PAu)-closo-2-CB(9)H(9)](-) (3) with gold-carbon 2c-2e sigma bonds have been prepared from [AuCl(PPh(3))] and the respective carba-closo-borate dianion. The anions have been isolated as their Cs(+) salts and the corresponding [Et(4)N](+) salts were obtained by salt metathesis reactions. The salt Cs-3 isomerizes in the solid state and in solution at elevated temperatures to Cs-2 with DeltaH(iso)=(-75+/-5) kJ mol(-1) (solid state) and DeltaH( not equal)=(118+/-10) kJ mol(-1) (solution). The compounds were characterized by vibrational and multi-NMR spectroscopies, mass spectrometry, elemental analysis, and differential scanning calorimetry. The crystal structures of [Et(4)N]-1, [Et(4)N]-2, and [Et(4)N]-3 were determined. The bonding parameters, NMR chemical shifts, and the isomerization enthalpy of Cs-3 to Cs-2 are compared to theoretical data.

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Section: N]mentioning

confidence: 95%

Section: àmentioning

confidence: 99%

Section: àmentioning

confidence: 99%

“…[7,53] . [18] Thermal isomerization of Cs[closo-2-CB 9 H 10 ] resulted in Cs[closo-1-CB 9 H 10 ]. [18,55] Decaborane (14) À (3), and related carba-closo-borate anions.…”

mentioning

confidence: 99%

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Anionic Gold(I) Complexes—Twelve‐ and Ten‐Vertex Monocarba‐closo‐borate Anions with Carbon–Gold σ Bonds

Finze

Sprenger

2009

Chemistry A European J

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“…These may then be converted, via cluster-dismantling or cluster-Aufbau protocols, into a variety of {CB 6 }, {CB 7 }, {CB 8 }, {CB 10 } and {CB 11 } monocarbaborane systems [20][21][22][23]. For example, the simplest initial monocarbaborane so formed, the [arachno-6-CB 9 H 14 ] À anion, may in this manner be prepared in 64% yield from nido-B 10 H 14 and formaldehyde, HCHO [24,25]. Obviously, the reaction involves the loss of one boron vertex.…”

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confidence: 99%

Polyhedral dicarbaborane chemistry: a convenient synthesis of the [nido-7,8-C2B9H12]− ‘dicarbollide’ anion via the Brellochs reaction

Franken¹,

Kennedy²

2005

Inorganic Chemistry Communications

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Quantum‐Chemical and Electrochemical Investigation of the Electrochemical Windows of Halogenated Carborate Anions

Boeré

Bolli

Finze

et al. 2012

Chemistry A European J

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The range of electrochemical stability of a series of weakly coordinating halogenated (Hal=F, Cl, Br, I) 1-carba-closo-dodecaborate anions, [1-R-CB(11)X(5)Y(6)](-) (R=H, Me; X=H, Hal, Me; Y=Hal), has been established by using quantum chemical calculations and electrochemical methods. The structures of the neutral and dianionic radicals, as well as the anions, have been optimized by using DFT calculations at the PBE0/def2-TZVPP level. The calculated structures are in good agreement with existing experimental data and with previous calculations. Their gas-phase ionization energies and electron affinities were calculated based on their optimized structures and were compared with experimental (cyclic and square-wave) voltammetry data. Electrochemical oxidation was performed in MeCN at room temperature and in liquid sulfur dioxide at lower temperatures. All of the anions show a very high resistance to the onset of oxidation (2.15-2.85 V versus Fc(0/+)), with only a minor dependence of the oxidation potential on the different halogen substituents. In contrast, the reduction potentials in MeCN are strongly substituent dependent (-1.93 to -3.32 V versus Fc(0/+)). The calculated ionization energies and electron affinities correlate well with the experimental redox potentials, which provide important verification of the thermodynamic validity of the mostly irreversible redox processes that are observed for this series. The large electrochemical windows that are afforded by these anions indicate their suitability for electrochemical applications, for example, as supporting electrolytes.

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Structural chemistry of halogenated monocarbaboranes: the extended structures of Cs[1-HCB₉H₄Br₅], Cs[1-HCB₁₁H₅Cl₆] and Cs[1-HCB₁₁H₅Br₆]

Cited by 42 publications

References 62 publications

Anionic Gold(I) Complexes—Twelve‐ and Ten‐Vertex Monocarba‐closo‐borate Anions with Carbon–Gold σ Bonds

Anionic Gold(I) Complexes—Twelve‐ and Ten‐Vertex Monocarba‐closo‐borate Anions with Carbon–Gold σ Bonds

Polyhedral dicarbaborane chemistry: a convenient synthesis of the [nido-7,8-C2B9H12]− ‘dicarbollide’ anion via the Brellochs reaction

Quantum‐Chemical and Electrochemical Investigation of the Electrochemical Windows of Halogenated Carborate Anions

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