Synthesis, Properties, and Derivatization of Poly(dihydrogermane): A Germanium-Based Polyethylene Analogue

Abstract

Polygermanes are germanium-based analogues of polyolefins and possess polymer backbones made up catenated Ge atoms. In the present contribution we report the preparation of a stable germanium polyethylene analogue -polydihydrogermane (i.e., (GeH2)n) -via two straightforward approaches that involve topotactic deintercalation of the CaGe Zintl phase. The resulting (GeH2)n possess morphologically dependent chemical and electronic properties and thermally decompose to yield amorphous hydrogenated Ge. We also show that the resulting (GeH2)n provide a platform from which functionalized polygermanes can be prepared via thermally-induced hydrogermylation-mediated pendant group substitution. This facile one-step derivatization reaction exploits Ge-H reactivity and opens the door to a wide array of tailored functional polygermanes.

Frustrated Lewis pair-ligated tetrelenes

“…of Li[HBEt 3 ] in Et 2 O at room temperature (Scheme 7). Analysis of the soluble reaction products by 1 H, 31 P and 11 B NMR spectroscopy confirmed the quantitative conversion of 11 into free CH2 PB Mes , 24 suggesting that the intended product [ i Pr 2 PCH 2 (C 6 H 4 )BMes 2 {GeH 2 }] ( 12 ) is significantly less stable than the known Ge( ii ) dihydride adduct [PB{GeH 2 }] ( 4 ). 7…”

2D Functionalized Germananes: Synthesis and Applications

“…Yu et al [94] 19 BnGe/Cr(CO) 6 /UV BnGe/Mo(CO) 6 /UV BnGe/W(CO) 6 /UV BnGe was prepared according to Sturala et al [63] GeH or BnGe was dispersed in anhydrous THF and added by M(CO) 6 (M = Cr, Mo, W), then stirred at RT for 3 h under argon atmosphere with photo-irradiation.…”

“…[ 63 ] j) Fluorescence spectra of functionalized germananes; inset shows the dispersion of Ge‐4FPh_B after irradiation with a UV lamp, λ = 254 nm. [ 93 ] k) Schematic illustration of the (200) reflection of CaGe and (GeH 2 ) n , showing ≈20% space compression by substituting Ca with H. [ 94 ] a‐i,a‐iii) Reproduced with permission. [ 54 ] Copyright 2013, American Chemical Society.…”

“…Copyright 2019, Royal Society Chemistry. k) Reproduced with permission [94]. Copyright 2021, American Chemical Society.…”

Oligoorganogermanes: Interplay between Aryl and Trimethylsilyl Substituents

“…Compounds of this type can be molecular or polymeric. Molecular derivatives can be regarded as models for polymers and “hybrid” materials based on them [ 12 , 13 , 14 ], including molecular conductors [ 15 ] and semiconductors [ 16 ]. Furthermore, catenated group 14 element derivatives can be used as synthetic reagents.…”