Formation and Reactions of Ge=O Double-bonded Species Bearing EMind Groups

Kuroda, Airi; Fujita, Naoko; Horita, Tomomi; Ota, Kei; Rosas-Sánchez, Alfredo; Hoshino, Manabu; Hashizume, Daisuke; Matsuo, Tsukasa

doi:10.1246/cl.220222

Cited by 2 publications

(2 citation statements)

References 39 publications

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“…These compounds were obtained as purple-to-blue crystals at room temperature by the reaction of GeCl 2 •dioxane with two equivalents of (Rind)Li, and their structures were determined by an X-ray crystallographic analysis. Notably, the bulky Eind-based germylene, (Eind) 2 Ge: (M-b), reacted with trimethylamine N-oxide (Me 3 N + -O -) or N 2 O gas to afford an isolable monomeric germanone, (Eind) 2 Ge=O, with the planar three-coordinate Ge(IV) atom and a terminal oxygen atom [31,33]. Additionally, we successfully isolated a Sn(II) analog, diarylstannylene, (EMind) 2 Sn: (N-a), as purple crystals by a similar reaction of SnBr 2 •dioxane with two equivalents of (EMind)Li [34].…”

Section: Resultsmentioning

confidence: 99%

Approach to the “Missing” Diarylsilylene: Formation, Characterization, and Intramolecular C–H Bond Activation of Blue Diarylsilylenes with Bulky Rind Groups

Mochihara,

Morimoto,

Ota

et al. 2024

IJMS

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The treatment of the bulky Rind-based dibromosilanes, (Rind)2SiBr2 (2) [Rind = 1,1,7,7-tetra-R1-3,3,5,5-tetra-R2-s-hydrindacen-4-yl: EMind (a: R1 = Et, R2 = Me) and Eind (b: R1 = R2 = Et)], with two equivalents of tBuLi in Et2O at low temperatures resulted in the formation of blue solutions derived from the diarylsilylenes, (Rind)2Si: (3). Upon warming the solutions above −20 °C, the blue color gradually faded, accompanying the decomposition of 3 and yielding cyclic hydrosilanes (4) via intramolecular C–H bond insertion at the Si(II) center. The molecular structures of the bulky Eind-based 3b and 4b were confirmed by X-ray crystallography. Thus, at −20 °C, blue crystals were formed (Crystal-A), which were identified as mixed crystals of 3b and 4b. Additionally, colorless crystals of 4b as a singular component were isolated (Crystal-B), whose structure was also determined by an X-ray diffraction analysis. Although the isolation of 3 was difficult due to their thermally labile nature, their structural characteristics and electronic properties were discussed based on the experimental findings complemented by computational results. We also examined the hydrolysis of 3b to afford the silanol, (Eind)2SiH(OH) (5b).

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Section: Resultsmentioning

confidence: 99%

Approach to the “Missing” Diarylsilylene: Formation, Characterization, and Intramolecular C–H Bond Activation of Blue Diarylsilylenes with Bulky Rind Groups

Mochihara,

Morimoto,

Ota

et al. 2024

IJMS

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“…[8] Matsuo, Tamao, et al. have synthesized the first base‐ and donor‐free Ge=O species that have three‐coordinate unsaturated germanium atom stabilized by bulky aryl groups ( B ) [9a] and recently they also reported the synthesis of a pyridine‐coordinated germanone having structurally‐similar less bulky aryl substituents [9b] . Nagendran reported donor/accepter‐stabilized germacarboxylic acid derivatives C [10] .…”

Section: Introductionmentioning

confidence: 99%

An Isolable THF‐Coordinated Dialkylgermanone

Oshima,

Kobayashi,

Sakamoto

et al. 2024

Chemistry An Asian Journal

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A stable dialkylgermanone was generated by mixing a solid of the corresponding dialkylgermylene and gaseous N2O. While the dialkylgermanone is marginally persistent in solution and gradually converts to its head‐to‐tail dimer at room temperature, the addition of THF to the dialkylgermanone provided an isolable THF‐coordinated dialkylgermanone. The THF‐coordinated dialkylgermanone reacts with H2O, THF, and B(C6F5)3 similar to the corresponding base‐free two‐coordinate dialkylsilanone. The dialkylgermanone undergoes deoxygenation in the presence of triphenylphosphine to provide the corresponding germylene and olefination upon treatment with phosphaylide Ph3PCHPh to afford the corresponding Ge=C bond compound (germa‐Wittig reaction).

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Formation and Reactions of Ge=O Double-bonded Species Bearing EMind Groups

Cited by 2 publications

References 39 publications

Approach to the “Missing” Diarylsilylene: Formation, Characterization, and Intramolecular C–H Bond Activation of Blue Diarylsilylenes with Bulky Rind Groups

Approach to the “Missing” Diarylsilylene: Formation, Characterization, and Intramolecular C–H Bond Activation of Blue Diarylsilylenes with Bulky Rind Groups

An Isolable THF‐Coordinated Dialkylgermanone

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