[[(Me₃Si)₂CH]₂^<i>i</i>PrSi(NHC)SiSi(Me)Si^<i>i</i>Pr[CH(SiMe₃)₂]₂]⁺: A Molecule with Disilenyl Cation Character

Reaction of the disilyne–NHC complex <b>1</b> [RLSiSiR: (R = Si^<i>i</i>Pr­[CH­(SiMe₃)₂]₂, L = NHC)] with MeOTf gave the cation <b>2</b> [RLSiSiRMe]⁺, which is the first example of a base-stabilized heavy group 14 element analogue with vinyl cation character. Cation <b>2</b> has been fully characterized by multinuclear NMR spectroscopy and X-ray diffraction analysis. The molecular structure indicates that there are significant contributions from the NHC-stabilized cationic resonance structure <b>2A</b>, the disilene-like structure <b>2B</b>, and even some contribution from the silylene-like structure <b>2C</b>

[[(Me₃Si)₂CH]₂^<i>i</i>PrSi(NHC)SiSi(Me)Si^<i>i</i>Pr[CH(SiMe₃)₂]₂]⁺: A Molecule with Disilenyl Cation Character

Reaction of the disilyne–NHC complex <b>1</b> [RLSiSiR: (R = Si^<i>i</i>Pr­[CH­(SiMe₃)₂]₂, L = NHC)] with MeOTf gave the cation <b>2</b> [RLSiSiRMe]⁺, which is the first example of a base-stabilized heavy group 14 element analogue with vinyl cation character. Cation <b>2</b> has been fully characterized by multinuclear NMR spectroscopy and X-ray diffraction analysis. The molecular structure indicates that there are significant contributions from the NHC-stabilized cationic resonance structure <b>2A</b>, the disilene-like structure <b>2B</b>, and even some contribution from the silylene-like structure <b>2C</b>

Observation of Room Temperature B–Cl Activation of the HCB₁₁Cl₁₁^– Anion and Isolation of a Stable Anionic Carboranyl Phosphazide

The perchlorinated carba-<i>closo</i>-dodecaborate anion is typically inert toward B–Cl functionalization. We present here the observation of two competing reactions that occur with this anion at ambient temperature. When this molecule is treated with <i>n</i>-BuLi and subsequently reacted with tosyl azide, a cycloaddition occurs and results in chloride substitution at a B–Cl vertex. The competing and dominant pathway is a substitution reaction to form the azide N₃CB₁₁Cl₁₁^–. This rare anionic carboranyl azide reacts with PPh₃ in FC₆H₅ to afford a stable anionic phosphazide. When dissolved in tetrahydrofuran, the phosphazide is in equilibrium with free PPh₃ and N₃CB₁₁Cl₁₁^–. Both the triazole and phosphazide are characterized by single-crystal X-ray diffraction, NMR and IR spectroscopy, and high-resolution mass spectrometry

Observation of Room Temperature B–Cl Activation of the HCB₁₁Cl₁₁^– Anion and Isolation of a Stable Anionic Carboranyl Phosphazide

The perchlorinated carba-<i>closo</i>-dodecaborate anion is typically inert toward B–Cl functionalization. We present here the observation of two competing reactions that occur with this anion at ambient temperature. When this molecule is treated with <i>n</i>-BuLi and subsequently reacted with tosyl azide, a cycloaddition occurs and results in chloride substitution at a B–Cl vertex. The competing and dominant pathway is a substitution reaction to form the azide N₃CB₁₁Cl₁₁^–. This rare anionic carboranyl azide reacts with PPh₃ in FC₆H₅ to afford a stable anionic phosphazide. When dissolved in tetrahydrofuran, the phosphazide is in equilibrium with free PPh₃ and N₃CB₁₁Cl₁₁^–. Both the triazole and phosphazide are characterized by single-crystal X-ray diffraction, NMR and IR spectroscopy, and high-resolution mass spectrometry

Observation of Room Temperature B–Cl Activation of the HCB₁₁Cl₁₁^– Anion and Isolation of a Stable Anionic Carboranyl Phosphazide

The perchlorinated carba-<i>closo</i>-dodecaborate anion is typically inert toward B–Cl functionalization. We present here the observation of two competing reactions that occur with this anion at ambient temperature. When this molecule is treated with <i>n</i>-BuLi and subsequently reacted with tosyl azide, a cycloaddition occurs and results in chloride substitution at a B–Cl vertex. The competing and dominant pathway is a substitution reaction to form the azide N₃CB₁₁Cl₁₁^–. This rare anionic carboranyl azide reacts with PPh₃ in FC₆H₅ to afford a stable anionic phosphazide. When dissolved in tetrahydrofuran, the phosphazide is in equilibrium with free PPh₃ and N₃CB₁₁Cl₁₁^–. Both the triazole and phosphazide are characterized by single-crystal X-ray diffraction, NMR and IR spectroscopy, and high-resolution mass spectrometry