Copper‐Mediated CC Cross‐Coupling Reaction of Monocarba‐<i>closo</i>‐dodecaborate Anion for the Synthesis of Functional Molecules

Kanazawa, Junichiro; Takita, Ryo; Jankowiak, Aleksandra; Fujii, Shinya; Kagechika, Hiroyuki; Hashizume, Daisuke; Shudo, Koichi; Kaszyński, Piotr; Uchiyama, Masanobu

doi:10.1002/ange.201302448

Cited by 10 publications

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“…26,27 In addition, monocarba-closododecaboranyl metal complexes with a metal−C cluster σ-bond are intermediates in some functionalizations at the C cluster vertex, e.g., in the copper-mediated C cluster −C cross-coupling reaction. 28 In this contribution we report first on doubly negatively charged di(carba-closo-dodecaboranyl) mercury(II) complexes with functional groups. The functional groups are alkynyl substituents that are bonded to the antipodal boron atoms of the carboranyl ligands.…”

Section: ■ Introductionmentioning

confidence: 99%

Salts of the Dianions [Hg(12-X-closo-1-CB₁₁H₁₀)₂]^2– (X = I, C≡CH, C≡CFc, C≡CSiiPr₃): Synthesis and Spectroscopic and Structural Characterization

et al. 2015

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Cesium or tetraethylammonium salts of the doubly negatively charged mercury(II) complexes [Hg(12-I-closo-1-CB 11 H 10 ) 2 ] 2− (1), [Hg(12-HCC-closo-1-CB 11 H 10 ) 2 ] 2− (2), [Hg-(12-FcCC-closo-1-CB 11 H 10 ) 2 ] 2− (3), and [Hg(12-iPr 3 SiCCcloso-1-CB 11 H 10 ) 2 ] 2− (4) were synthesized. The synthesis of the alkynyl-functionalized clusters was conducted via two different routes. The alkynyl moiety either was present before formation of the mercury(II) complex or was introduced via a Pd-catalyzed crosscoupling reaction using Cs 2 1 as starting material. The compounds were characterized by multi-NMR and vibrational spectroscopy, mass spectrometry, and elemental analysis. Gas-phase reactions of the dianions 1, 2, and 3 were studied by collision-induced dissociation in (−)-ESI mass spectrometry experiments. Single crystals of Cs, and [Et 4 N] 2 3 were studied by X-ray diffraction. In the crystals of Cs 2 1•xMe 2 CO (x ≈ 2) the dianions and half of the Cs + cations form a stacked hexagonal structure with channels that contain the second half of the Cs + cations and the solvent molecules. The formation of this supramolecular structure is rationalized by weak Hg•••I and Cs•••I interactions that are close to classical van der Waals interactions.

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Section: ■ Introductionmentioning

confidence: 99%

Salts of the Dianions [Hg(12-X-closo-1-CB₁₁H₁₀)₂]^2– (X = I, C≡CH, C≡CFc, C≡CSiiPr₃): Synthesis and Spectroscopic and Structural Characterization

et al. 2015

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“Dumbbell”‐ and “Clackers”‐Shaped Dimeric Derivatives of Monocarba‐closo‐dodecaborate

et al. 2018

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We designed, synthesized, and characterized two types of dimeric forms of monocarba-closo-dodecaborate, namely,a"dumbbell"-shaped dianion having aC ÀCbond and a" clackers"-shaped monoanion having an iodonium linker. The unique architectures of these anionic molecules were established by X-ray analysis.S pectroscopic analysis,D FT calculations,a nd reactivity experiments revealed high anionic and chemical stability of both anions,w hich are crucial properties for weakly coordinating anions.

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A 3D Analogue of Phenyllithium: Solution‐Phase, Solid‐State, and Computational Study of the Lithiacarborane [Li−CB₁₁H₁₁]⁻

et al. 2019

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The lithiacarborane [LiÀCB 11 H 11 ] À playsacentral role in carborane chemistry,a si ti sakey intermediate to achieve the selective functionalization of the monocarba-closododecaborate [CB 11 H 12 ] À for applications in various fields. Also,i ti sa no rganometallic species of fundamental interest because it represents a3Danalogue of phenyllithium featuring an exo CÀLi bond in addition to the delocalized negative endo charge of the spherical cluster.For the first time,the elusive and highly reactive endo/exo formal dianion [CB 11 H 11 ] 2À has been isolated as its lithiate as well as zincate in pure form and fully characterized.D FT calculations corroborate the experimental findings and underscore the remarkably high reactivity of the lithiacarborane.S ubsequent derivatizations demonstrate the relevance of its initial clean formation.

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Copper‐Mediated CC Cross‐Coupling Reaction of Monocarba‐closo‐dodecaborate Anion for the Synthesis of Functional Molecules

Cited by 10 publications

References 54 publications

Salts of the Dianions [Hg(12-X-closo-1-CB₁₁H₁₀)₂]^2– (X = I, C≡CH, C≡CFc, C≡CSiiPr₃): Synthesis and Spectroscopic and Structural Characterization

Salts of the Dianions [Hg(12-X-closo-1-CB₁₁H₁₀)₂]^2– (X = I, C≡CH, C≡CFc, C≡CSiiPr₃): Synthesis and Spectroscopic and Structural Characterization

“Dumbbell”‐ and “Clackers”‐Shaped Dimeric Derivatives of Monocarba‐closo‐dodecaborate

A 3D Analogue of Phenyllithium: Solution‐Phase, Solid‐State, and Computational Study of the Lithiacarborane [Li−CB₁₁H₁₁]⁻

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Copper‐Mediated CC Cross‐Coupling Reaction of Monocarba‐closo‐dodecaborate Anion for the Synthesis of Functional Molecules

Cited by 10 publications

References 54 publications

Salts of the Dianions [Hg(12-X-closo-1-CB11H10)2]2– (X = I, C≡CH, C≡CFc, C≡CSiiPr3): Synthesis and Spectroscopic and Structural Characterization

Salts of the Dianions [Hg(12-X-closo-1-CB11H10)2]2– (X = I, C≡CH, C≡CFc, C≡CSiiPr3): Synthesis and Spectroscopic and Structural Characterization

“Dumbbell”‐ and “Clackers”‐Shaped Dimeric Derivatives of Monocarba‐closo‐dodecaborate

A 3D Analogue of Phenyllithium: Solution‐Phase, Solid‐State, and Computational Study of the Lithiacarborane [Li−CB11H11]−

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Salts of the Dianions [Hg(12-X-closo-1-CB₁₁H₁₀)₂]^2– (X = I, C≡CH, C≡CFc, C≡CSiiPr₃): Synthesis and Spectroscopic and Structural Characterization

Salts of the Dianions [Hg(12-X-closo-1-CB₁₁H₁₀)₂]^2– (X = I, C≡CH, C≡CFc, C≡CSiiPr₃): Synthesis and Spectroscopic and Structural Characterization

A 3D Analogue of Phenyllithium: Solution‐Phase, Solid‐State, and Computational Study of the Lithiacarborane [Li−CB₁₁H₁₁]⁻