ChemInform Abstract: Organoboration of Alkinylstannanes. Part 16. Borol Synthesis via Organoboration of Bis(alkinyl)boranes.

Sebald, Angelika; Wrackmeyer, B.

doi:10.1002/chin.198702277

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“…Among metalloles with group 13 elements (Scheme ), borole (boracyclopentadiene) derivatives, R 1 EC 4 R 2 4 (E = B), have attracted significant attention owing to their academic and industrial importance . Borole derivatives have been investigated for decades to fully understand their structure, reactivity, strength of Lewis acidity, 3 and π-conjugation . Boroles are generally unstable at ambient temperature without bulky substituents on the boron atoms and cyclic skeletons, or coordination of Lewis base on the boron atoms.…”

Section: Introductionmentioning

confidence: 99%

Ten-Membered Cyclodecatetraene Derivatives Including Two Gallium Atoms: Experimental and Theoretical Studies on Synthesis, Structures, and Their Transformations to Nine- and Five-Membered Gallacycles

et al. 2023

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The chemistry of medium-sized ring compounds, including group 13 elements, has scarcely been investigated. Herein, we report that 5,10-digallacyclodeca-1,3,6,8-tetraene derivatives Cl 2 Ga 2 C 8 R 8 (R = Me (5a), Et (5b)) can be obtained by the reaction of GaCl 3 and zirconacyclopentadiene Cp 2 ZrC 4 R 4 (R = Me (2a), Et (2b), Cp: η 5 -C 5 H 5 ) in toluene. X-ray crystal structure analysis revealed that compound 5b has a 10-membered cyclodecatetraene structure composed of two butadiene skeletons and two GaCl fragments. X-ray crystal structure analysis and IR measurement confirmed that compound 5b forms Ga 2 Cl 2 four-membered rings via intermolecular Cl to Ga donor−acceptor interactions, which result in the formation of oligomeric chain structures in the solid state and toluene solution. The treatment of compound 5b with 2 equivalents of 4-(dimethylamino)pyridine (DMAP) proceeded via the coordination of DMAP to the Ga center and the ring contraction to give DMAP-coordinated five-membered gallole Cl(DMAP)GaC 4 Et 4 (4bDMAP). The reaction of compound 5a with 2 equivalents of MesLi (Mes: 2,4,6-Me 3 C 6 H 2 ) in toluene to form a 9,10-digallabicyclo[4.3.1]decatriene derivative (MesGaC 8 Me 8 )GaMes (6a) caused ring contraction. Theoretical investigation revealed that the 10-membered ring derivative, Cl 2 Ga 2 C 8 H 8 (GaH-10), is formed by the dimerization of two gallole molecules, ClGaC 4 H 4 (GaH-5), via the addition of two Ga−C bonds without an energy barrier. The immediate formation of GaH-10 was attributed to the transannular electronic interaction between the expanded empty p-orbital on the Ga atom and the electron-rich sp 2 carbons of the C�C double bond in GaH-5. Moreover, GaH-10 and one of the isomer, nine-membered ring derivative (ClGaC 8 H 8 )GaCl, were found to be thermodynamically more stable, as compared to GaH-5.

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Section: Introductionmentioning

confidence: 99%

Ten-Membered Cyclodecatetraene Derivatives Including Two Gallium Atoms: Experimental and Theoretical Studies on Synthesis, Structures, and Their Transformations to Nine- and Five-Membered Gallacycles

et al. 2023

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ChemInform Abstract: Organoboration of Alkinylstannanes. Part 16. Borol Synthesis via Organoboration of Bis(alkinyl)boranes.

Abstract: 277ChemInform Abstract Treatment of the borane (I) with the diethylaminostannane (II) yieldsthe stannylborane (III) which reacts with triethylborane (IV) to form (V). Refluxing in benzene causes isomerization of (V) to the borol (VII) via (VI). (IR-, 1H-, 11B-, 13C-, 119Sn-NMRdata).

Cited by 1 publication

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Ten-Membered Cyclodecatetraene Derivatives Including Two Gallium Atoms: Experimental and Theoretical Studies on Synthesis, Structures, and Their Transformations to Nine- and Five-Membered Gallacycles

Ten-Membered Cyclodecatetraene Derivatives Including Two Gallium Atoms: Experimental and Theoretical Studies on Synthesis, Structures, and Their Transformations to Nine- and Five-Membered Gallacycles

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