1,2-Dihalodigermenes bearing bulky Eind groups: synthesis, characterization, and conversion to halogermylenoids

Naoki Hayakawa; Tomohiro Sugahara; Yasuyuki Numata; Hotaka Kawaai; Kenta Yamatani; Shogo Nishimura; Shun Goda; Yuko Suzuki; Tomoharu Tanikawa; Hidetaka Nakai; Daisuke Hashizume; Takahiro Sasamori; Norihiro Tokitoh; Tsukasa Matsuo

doi:10.1039/C7DT03819D

1,2-Dihalodigermenes bearing bulky Eind groups: synthesis, characterization, and conversion to halogermylenoids†

Naoki Hayakawa,^a Tomohiro Sugahara,^b Yasuyuki Numata,^a Hotaka Kawaai,^a Kenta Yamatani,^a Shogo Nishimura,^a Shun Goda,^a Yuko Suzuki,^b Tomoharu Tanikawa,^a Hidetaka Nakai,

^a Daisuke Hashizume,

^c Takahiro Sasamori,

*^bd Norihiro Tokitoh

^b and Tsukasa Matsuo

*^a

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* Corresponding authors

^a Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University, 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan
E-mail: t-matsuo@apch.kindai.ac.jp

^b Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan

^c Materials Characterization Support Unit, RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan

^d Graduate School of Natural Sciences, Nagoya City University, Yamanohata 1, Mizuho-cho, Mizuho-ku, Nagoya, Aichi 467-8501, Japan
E-mail: sasamori@nsc.nagoya-cu.ac.jp

Abstract

1,2-Dihalodigermenes, (E)-(Eind)XGe [double bond, length as m-dash] GeX(Eind) (X = Br and Cl), bearing the fused-ring bulky Eind group (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl) have been isolated as orange-yellow crystals by the ligand redistribution reaction between the diarylgermylene, (Eind)₂Ge:, and GeX₂·dioxane in toluene via the cleavage and recombination of the Ge–C and Ge–X bonds. The dihalodigermenes have a Ge [double bond, length as m-dash] Ge double bond character in the crystalline state, but dissociate into halogermylenes, (Eind)XGe:, in solution. The addition of excess LiBr to the THF solution of the bromogermylene, (Eind)BrGe:, led to the formation of an equilibrium mixture containing the lithium bromogermylenoid, [Li⁺][(Eind)GeBr₂]⁻. The bromogermylenoid can be isolated as a cryptand-separated potassium ion pair, [K⁺(crypt-222)][(Eind)GeBr₂]⁻, which has been structurally characterized.

Dalton Transactions

1,2-Dihalodigermenes bearing bulky Eind groups: synthesis, characterization, and conversion to halogermylenoids†

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1,2-Dihalodigermenes bearing bulky Eind groups: synthesis, characterization, and conversion to halogermylenoids

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