12-(N-Methylnitrilium)monocarba-closo-dodecaborate Ylide

Šembera, Filip; Higelin, Alexander; Cı́sařová, Ivana; Michl, Josef

doi:10.5562/cca2475

Cited by 7 publications

(3 citation statements)

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“…In contrast, 2 is quite reactive as a Lewis base. Under the conditions used for methylation of the carborane cage (sulfolane with CaH 2 and MeOTf at 25 °C), or upon treatment with trimethyloxonium tetrafluoroborate in CH 3 NO 2 , methylation occurs selectively on the nitrogen atom of the cyano group of 2 and gives an N- methylnitrilium ylide . Under these conditions, methylation at the boron vertices was not detected.…”

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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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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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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“…Boron clusters with cyano groups bonded to one or more B atoms have been described, and different synthetic methods for B cluster −CN‐containing derivatives have been developed . They serve as starting materials for 1) the preparation of boron clusters with other functional groups, 2) cluster Aufbau reactions by insertion of the C atom of the CN group into the boron cage, and 3) as ligands in coordination chemistry . So far, the [3‐NC‐ closo ‐B 11 F 10 ] 2− anion is the only example of a { closo ‐B 11 } cluster with a CN substituent, and { nido ‐B 11 } derivatives are unknown.…”

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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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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“…10–15% by MS), and it was not isolated. An alternate approach to cyanation, by transition-metal cross-coupling reactions, has been demonstrated with closo -CB 11 – clusters , and closo -C 2 B 10 clusters but never with the isoelectronic B 12 2– cluster. We report here a microwave-promoted cross-coupling method for the preparation of 2 and the isolation, spectroscopic characterization, and X-ray crystal structure of this cluster.…”

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Exhaustive Cyanation of the Dodecaborate Dianion: Synthesis, Characterization, and X-ray Crystal Structure of [B₁₂(CN)₁₂]^2–

Kamin

Juhasz

2019

Inorg. Chem.

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The percyanated dodecaborate anion [B12(CN)12]2– was prepared by reacting [B12I12]2– with CuCN in the presence of a palladium catalyst at elevated pressure and temperature in a microwave reactor. The fully cyanated cluster was isolated as a tetraethylammonium salt in yields of up to 39% and characterized by NMR and IR spectroscopy and mass spectrometry. The crystal structure of a copper complex of the percyanated anion, (CH3CN)3Cu[μ-B12(CN)12]Cu(NCCH3)3, was determined by single-crystal X-ray diffraction.

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12-(N-Methylnitrilium)monocarba-closo-dodecaborate Ylide

Abstract: Abstract. The syntheses, spectral characterization, and crystal structures of 12-(N-methylnitrilium)-monocarba-closo-dodecaborate and 12-(N-methylamidinium)-monocarba-closo-dodecaborate ylides are reported. The carborate anion behaves as an inert and non-conjugating negative charge.

Cited by 7 publications

References 13 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)

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

Exhaustive Cyanation of the Dodecaborate Dianion: Synthesis, Characterization, and X-ray Crystal Structure of [B₁₂(CN)₁₂]^2–

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12-(N-Methylnitrilium)monocarba-closo-dodecaborate Ylide

Abstract: Abstract. The syntheses, spectral characterization, and crystal structures of 12-(N-methylnitrilium)-monocarba-closo-dodecaborate and 12-(N-methylamidinium)-monocarba-closo-dodecaborate ylides are reported. The carborate anion behaves as an inert and non-conjugating negative charge.

Cited by 7 publications

References 13 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)

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

Exhaustive Cyanation of the Dodecaborate Dianion: Synthesis, Characterization, and X-ray Crystal Structure of [B12(CN)12]2–

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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)

Exhaustive Cyanation of the Dodecaborate Dianion: Synthesis, Characterization, and X-ray Crystal Structure of [B₁₂(CN)₁₂]^2–