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

Dalton Trans. 2018 Jan 15;47(3):814-822. doi: 10.1039/c7dt03819d.

Authors

Naoki Hayakawa¹, 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

Affiliation

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

PMID: 29250632
DOI: 10.1039/c7dt03819d

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.