Formation of Alkynylgermyl-Substituted Germylenes via a Catenation of Ge Atoms

Chenghuan Liu; Keke Zhu; Weichun Han; Xue Liu; Zheng-Feng Zhang; Ming-Der Su; Di Wu; Yan Li

doi:10.1021/acs.inorgchem.0c01244

Formation of Alkynylgermyl-Substituted Germylenes via a Catenation of Ge Atoms

Inorg Chem. 2020 Jul 20;59(14):10123-10128. doi: 10.1021/acs.inorgchem.0c01244. Epub 2020 Jun 29.

Authors

Chenghuan Liu¹, Keke Zhu¹, Weichun Han¹, Xue Liu¹, Zheng-Feng Zhang², Ming-Der Su^{2

3}, Di Wu⁴, Yan Li¹

Affiliations

¹ Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, 311121, China.
² Department of Applied Chemistry, National Chiayi University, Chiayi, 60004, Taiwan.
³ Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung, 80708, Taiwan.
⁴ College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 311121, China.

PMID: 32598836
DOI: 10.1021/acs.inorgchem.0c01244

Abstract

Reactions of amidinate-stabilized germylene chlorides R¹Ge(:)Cl (R¹ = PhC(NtBu)₂) and R²Ge(:)Cl (R² = PhC(NCy)₂, Cy = cyclohexanyl) with trimethylsilylethynyl lithium salt (LLi, L = -C≡CTMS) afforded alkynylgermyl-substituted germylenes R¹(:)Ge-GeL₃ (1) and [R²GeL₂]₂Ge(:) (2), respectively. Both of them may undergo the formation of Ge-Ge single bonds with a concomitant 1,2-shift of ethynyl groups. DFT calculations determined the reaction pathways where two possible intermediates (:)GeL₂ and RGe(:)L (R = R¹, R²) are proposed, which were consistent with the trapping reactions of (:)GeL² toward I_Ar-(:)GeL² (3, I_Ar = :C{N(Ar)CH}₂, Ar = 2,6-iPr₂C₆H₃). The reaction of 1 with N₃TMS gave a new aminogermylene R¹(:)Ge-N(TMS)-GeL₃ (4), indicating a reactive Ge-Ge bond.