Issue 3, 2018

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

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.

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

Supplementary files

Article information

Article type
Paper
Submitted
11 Oct 2017
Accepted
07 Dec 2017
First published
08 Dec 2017

Dalton Trans., 2018,47, 814-822

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

N. Hayakawa, T. Sugahara, Y. Numata, H. Kawaai, K. Yamatani, S. Nishimura, S. Goda, Y. Suzuki, T. Tanikawa, H. Nakai, D. Hashizume, T. Sasamori, N. Tokitoh and T. Matsuo, Dalton Trans., 2018, 47, 814 DOI: 10.1039/C7DT03819D

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