Salts of the 1-cyanocarba-closo-dodecaborate anions [1-NC-closo-1-CB11X11]− (X = H, F, Cl, Br, I)

Finze, Maik; Sprenger, Jan A. P.; Schaack, Bernd Bastian

doi:10.1039/b922720b

Cited by 39 publications

(11 citation statements)

References 81 publications

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“…This salt is stable in air, but it degrades in aqueous NaOH or CsOH with loss of fluorine atoms. Similar behavior was previously reported for Cs[1-CN-CB 11 F 11 ] …”

Section: Resultssupporting

confidence: 88%

“…Similar behavior was previously reported for Cs[1-CN-CB 11 F 11 ]. 61 Compound 23 was prepared as a counterpart to 20 to examine the effect of electron-donating and electron-withdrawing groups on the carborane cage. Due to the electronwithdrawing effect of the fluorine atoms, the CN group of 23 is strongly deactivated and does not serve as electron donor for the preparation of nitrilium inner salts or complexes with transition metals.…”

Section: ■ Resultsmentioning

confidence: 99%

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Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC–CB₁₁X₁₁^– (X = H, F, CH₃) as Ligands on Pt(II) and Pd(II)

et al. 2016

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The anionic nitriles 1-R-12-NC-CB11H10(-) (R = H, CH3, I, COOH), 12-NC-1-H-CB11Me10(-), and 12-NC-1-H-CB11F10(-) were prepared, and three of them were examined for complex formation with (Et3P)2Pt(II) and (Et3P)2Pd(II). Several stable internally charge-compensated zwitterionic complexes were obtained and characterized. RI-BP86/SV(P) calculations suggest that their dipole moments exceed 20 D. An attempt to measure the dipole moments in solution failed due to insufficient solubility in solvents of low polarity.

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“…This salt is stable in air, but it degrades in aqueous NaOH or CsOH with loss of fluorine atoms. Similar behavior was previously reported for Cs[1-CN-CB 11 F 11 ] …”

Section: Resultssupporting

confidence: 88%

Section: ■ Resultsmentioning

confidence: 99%

Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC–CB₁₁X₁₁^– (X = H, F, CH₃) as Ligands on Pt(II) and Pd(II)

et al. 2016

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“…[3][4][5][6][7] The applications of these anions in chemistry have been well documented. [7][8][9][10][11][12][13][14][15][16][17][18][19][20] A significantly different class of weakly coordinating anions was recognized based on the remarkably stable boron cluster framework on monocarborane anions such as the icosahedral (I h ) carborane anion ([CHB 11 X 11 ] À ). It was first synthesized by Knoth at Du Pont in 1960s.…”

mentioning

confidence: 99%

Structure, stability and spectral signatures of monoprotic carborane acid–water clusters (CBWn, where n = 1–6)

Prakash

Subramanian

2011

Phys. Chem. Chem. Phys.

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The gas phase structure, stability, spectra, and proton transfer properties of monoprotic carborane acid-water clusters [CB(11)F(m)H(11-m)(OH(2))(1)]-(H(2)O)(n) (where m = 0, 5, and 10; n = 1-6) have been calculated using density functional theory (DFT) with the Becke's three-parameter hybrid exchange functional and Lee-Yang-Parr correlation functional (B3LYP) using 6-31+G* basis set. Results reveal that Eigen cation defects are found in CBW(n) (where n = 2-6) clusters and these clusters are significantly more stable than the non-Eigen geometry. In addition to the conventional hydrogen bond (H-bond) the role of dihydrogen bond (DHB) and halogen bond (XB) in the stabilization of these clusters can be observed from the molecular graphs derived from the atoms in molecules (AIM) analysis. Spectral information shows the features of Eigen cation and proton oscillation involved in the proton transfer process. The dissociation of proton from the perfluoro derivatives with two water molecules is more favorable when compared to the other derivatives.

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“…High yield C-cyanation of undecahalogenated carboranes has very recently been reported 15. These findings makes sense within the context of known carborane reactivity patterns.…”

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confidence: 66%

High Yield C-Derivatization of Weakly Coordinating Carborane Anions

Nava

Reed

2010

Inorg. Chem.

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Unlike the "parent" carborane anion CHB 11 H 11 − , halogenated carborane anions such as CHB 11 H 5 Br 6 − can be readily C-functionalized in high yield and purity, enhancing their utility as weakly coordinating anions.B-halogenated icosahedral carborane anions such as CHB 11 H 5 X 6 − and CHB 11 X 11 − (X = halogen) (Figure 1) are particularly useful members of a class of exceptionally inert, weakly coordinating anions 1-5 whose versatility might be further tailored by suitable C-derivatization chemistry. Long-chain hydrocarbon "tails" formed by C-alkylation should lower the lattice energies of salts, increase their solubilities in low dielectric solvents and allow better exploitation of reactive cations in catalysis. Applications in surfactant chemistry can also be envisioned. Similarly, C-fluorocarbon tails should improve the solubility of carborane ion pairs in fluorocarbon solvents, where catalytic applications have been reported. 6 Attachment of a carborane anion to a polymer has allowed exploitation of immobilization chemistry in cationselective sensor technology. 7 C-arylation takes advantage of the unique scaffold of a carborane anion in rigid rod supramolecular chemistry. 8,9 Despite these promising applications, the C-derivatization chemistry of carborane anions has progressed rather slowly. Most work has been performed on the "parent" carborane anion, CHB 11 H 11 − , but is frequently hampered by modest yields and difficult separations from starting material. Being ionic rather than neutral, the chromatographic separation of different carborane anions is not trivial on a synthetic scale. The activation of CHB 11 H 11 − via Clithiation with butyl lithium appears to be essentially quantitative 10 but the partial regeneration of starting material during subsequent reactions with electrophiles is common, despite careful control of conditions. Alkylation of 1-Li-CB 11 H 11 − with alkyl halides gives mixed results. While the yields for methylations are frequently quite high, 2,11-14 they drop to 63% for ethylation of CHB 11 H 11 − and are even lower for most other alkylations, silylations, phosphinations and metallations. 2,10 The yields of C-monohalogenated products, 1-X-CB 11 H 11 − , have been raised to 81-96% by careful attention to conditions but chromatography purification is still recommended for most derivatives. 11 We now report that when these C-functionalization reactions are performed on an already halogenated carborane anion such as CHB 11 H 5 Br 6 − , rather than on the unfunctionalized parent CHB 11 H 11 − , isolated yields are generally excellent and compound purity is sufficiently high

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Salts of the 1-cyanocarba-closo-dodecaborate anions [1-NC-closo-1-CB11X11]− (X = H, F, Cl, Br, I)

Cited by 39 publications

References 81 publications

Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC–CB₁₁X₁₁^– (X = H, F, CH₃) as Ligands on Pt(II) and Pd(II)

Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC–CB₁₁X₁₁^– (X = H, F, CH₃) as Ligands on Pt(II) and Pd(II)

Structure, stability and spectral signatures of monoprotic carborane acid–water clusters (CBWn, where n = 1–6)

High Yield C-Derivatization of Weakly Coordinating Carborane Anions

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Salts of the 1-cyanocarba-closo-dodecaborate anions [1-NC-closo-1-CB11X11]− (X = H, F, Cl, Br, I)

Cited by 39 publications

References 81 publications

Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC–CB11X11– (X = H, F, CH3) as Ligands on Pt(II) and Pd(II)

Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC–CB11X11– (X = H, F, CH3) as Ligands on Pt(II) and Pd(II)

Structure, stability and spectral signatures of monoprotic carborane acid–water clusters (CBWn, where n = 1–6)

High Yield C-Derivatization of Weakly Coordinating Carborane Anions

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Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC–CB₁₁X₁₁^– (X = H, F, CH₃) as Ligands on Pt(II) and Pd(II)

Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC–CB₁₁X₁₁^– (X = H, F, CH₃) as Ligands on Pt(II) and Pd(II)