Oligoorganogermanes: Interplay between Aryl and Trimethylsilyl Substituents

Abstract

Derivatives of main group elements containing element–element bonds are characterized by unique properties due to σ-conjugation, which is an attractive subject for investigation. A novel series of digermanes, Ar3Ge-Ge(SiMe3)3, containing aryl (Ar = p-C6H4Me (1), p-C6H4F (2), C6F5 (3)) and trimethylsilyl substituents, was synthesized by the reaction of germyl potassium salt, [(Me3Si)3GeK*THF], with triarylchlorogermanes, Ar3GeCl. The optical and electronic properties of such substituted oligoorganogermanes were investigated spectroscopically by UV/vis absorption spectroscopy and theoretically by DFT calculations. The molecular structures of compounds 1 and 2 were studied by XRD analysis. Conjugation between all structural fragments (Ge-Ge, Ge-Si, Ge-Ar, where Ar is an electron-donating or withdrawing group) was found to affect the properties.

Germanium Complexes with ONO Tridentate Ligands: O-H Bond Activation Control According to DFT Calculations

“…It should be noted that the parameters used for the calculations (B3LYP/DGDZVP for structure optimization) are correct; the main calculated structural parameters correlate well with the XRD data. In continuation of our research (see above, Schemes 1 and 3) into germylenes [33][34][35][42][43][44], this work presents our theoretical results on their synthesis to understand how the oxidation state of the central atom is regulated by the steric properties of organic ligands (1-H, 1-Me vs. 2-H, 2-Me), the oxidation state of which remains unchanged.…”

“…In continuation of our research (see above, Schemes 1 and 3) into germylenes [33][34][35][42][43][44], this work presents our theoretical results on their synthesis to understand how the oxidation state of the central atom is regulated by the steric properties of organic ligands (1-H, 1-Me vs. 2-H, 2-Me), the oxidation state of which remains unchanged. In continuation of our research (see above, Schemes 1 and 3) into germylenes [33][34][35][42][43][44], this work presents our theoretical results on their synthesis to understand how the oxidation state of the central atom is regulated by the steric properties of organic ligands (1-H, 1-Me vs. 2-H, 2-Me), the oxidation state of which remains unchanged.…”

“…In continuation of our research (see above, Scheme 1 and Scheme 3 ) into germylenes [ 33 , 34 , 35 , 42 , 43 , 44 ], this work presents our theoretical results on their synthesis to understand how the oxidation state of the central atom is regulated by the steric properties of organic ligands ( 1-H , 1-Me vs. 2-H , 2-Me ), the oxidation state of which remains unchanged.…”

“…Tetrylenes [3][4][5][6][7]-heavier carbene analogs-have recently attracted significant attention [8][9][10][11][12][13][14][15][16][17][18][19][20]), primarily due to their possible application as analogs of transition metals in catalysis [21][22][23], in activation of small molecules [24][25][26][27][28][29][30], as ligands [31,32], in possible synthesis of derivatives with E-E bonds [33][34][35], reagents for synthesis [36][37][38][39] or precursors [40][41][42] in material chemistry. These species are reactive and unstable; to stabilize them, the introduction of bulky groups (kinetic stabilization) or polydentate ligands (thermodynamic stabilization) is used.…”

Structural Motifs in Aryl Organogermanium Ge-O Derivatives for Material Design

“…At the same time, the effect of organic electron-withdrawing substituents on the Ge atom in related compounds strongly affects the structure of the molecule (causing a change in conformation; as a rule, a decrease in the values of valent bonds and angles; packing in more ordered structures) [25], which makes it important to study the impact of electron-withdrawing substituents on the structure and properties of the Ge-O-Ge molecule. This article is a continuation of our research program [26][27][28] on the effect of substituents on group 14 element derivatives on their structures and properties.…”