Selective synthesis of germasila-adamantanes through germanium–silicon shift processes

Kühn, Susanne; Koestler, Benedikt; True, C D; Albers, Lena; Marschner, Christoph; Müller, Thomas

doi:10.1039/d3sc03301e

Cited by 5 publications

(2 citation statements)

References 44 publications

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“…We note that the groups of Marschner, Wagner, and Muller have explored the synthesis of 1a and 4a in parallel with us. 36 Finally, we demonstrate the selective difunctional-ization of Ge centers over Si centers in adamantanes with mixed Si and Ge occupation at the bridgehead positions, allowing us to explore the implications of Ge-doping in both optical absorbance and quantum transport contexts.…”

Section: ■ Introductionmentioning

confidence: 52%

Installing Quaternary Germanium Centers in Sila-Diamondoid Cores via Skeletal Isomerization

Imex Aguirre Cardenas,

Siu,

Pimentel

et al. 2023

J. Am. Chem. Soc.

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This manuscript describes skeletal isomerization strategies to install one to four quaternary germanium atoms in the sila-adamantane core, in a cluster analogy to precision germanium doping in silicon–germanium alloys. The first strategy embodies an inorganic variant of single-atom skeletal editing, where we use a sila-Wagner-Meerwein bond shift cascade to exchange a peripheral Ge atom with a core Si atom. We can install up to four Ge atoms at the quaternary diamondoid centers based on controlling the Si x Ge y stoichiometry of our precursor. We find that bridgehead Ge centers can be selectively functionalized over bridgehead Si centers in SiGe adamantanes; we use this chemistry in conjunction with scanning tunneling microscopy break-junction (STM-BJ) measurements to show that Si8Ge2 adamantane wires give a 60% increase in single-molecule conductance compared with Si10 adamantanes. These studies describe the first quantum transport measurements in sila-diamondoid structures, and demonstrate how main-chain Ge doping can be used to increase electronic transmission in sila-diamondoid-based molecular wires.

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Section: ■ Introductionmentioning

confidence: 52%

Installing Quaternary Germanium Centers in Sila-Diamondoid Cores via Skeletal Isomerization

Imex Aguirre Cardenas,

Siu,

Pimentel

et al. 2023

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…We note that the groups of Marschner, Wagner, and Müller have reported similar results in parallel with us. 36 Finally, we demonstrate the selective di-functionalization of Ge centers over Si centers in adamantanes with mixed Si & Ge occupation at the bridgehead positions, allowing us to explore the implications of Ge-doping in both optical absorbance and quantum transport contexts.…”

Section: Figurementioning

confidence: 94%

Installing Quaternary Germanium Centers in Sila-Diamondoid Cores via Skeletal Isomerization

Cardenas

Siu

Pimentel

et al. 2023

Preprint

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This manuscript describes skeletal isomerization strategies to install one to four quaternary germanium atoms in the sila-adamantane core, in a cluster analogy to precision germanium doping in silicon-germanium alloys. The first strategy embodies an inorganic variant of single-atom skeletal editing, where we use a sila-Wagner-Meerwein bond shift cascade to exchange a peripheral Ge atom with a core Si atom. We can install up to four Ge atoms at the quaternary diamondoid centers based on controlling the SixGey stoichiometry of our precursor. We find that bridgehead Ge centers can be selectively functionalized over bridgehead Si centers in SiGe adamantanes; we use this chemistry in conjunction with scanning tunneling microscopy break-junction (STM-BJ) measurements to show that Si8Ge2 adamantane wires give a 60% increase in single-molecule conductance compared to Si10 adamantanes. These are the first quantum transport measurements in sila-diamondoid structures, and highlight how main-chain Ge doping can be used to increase electronic transmission in sila-diamondoid-based molecular wires.

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Adjusting the Number of Functional Groups in Vicinal Bis(trichlorosilylated) Benzenes

Schmidt,

Gilmer,

Virovets

et al. 2024

Chemistry A European J

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Organo(chloro)silanes are essential chemicals, but the synthesis of compounds of the formula RnSiCl4−n with defined values of n is usually laborious. Herein, we first disclose that a [4+2]‐cycloaddition between readily available Cl3SiC≡CSiCl3 and selected dienes provides facile access to vicinal bis(trichlorosilylated) benzenes and bicyclo[2.2.2]octa‐2,5‐dienes. Second, we show how the number of six Si−Cl bonds in 1,2‐(Cl3Si)2C6H2Me2 (1) can be selectively reduced to four or two by reaction with pinacol (H2pin) or catechol (H2cat), which act as Si⋅⋅⋅Si’‐bridging and/or Si‐chelating ligands. Third, we demonstrate that the thermolysis of compound 6, which contains a benzannulated eight‐membered C2(SiCl2)2(μ‐pin) ring with Si⋅⋅⋅Si’‐bridging pin moiety, furnishes 13 with a benzannulated five‐membered C2(SiCl2)2O ring via the release of pinacolone. Such cyclic disiloxanes are valuable building blocks for specialty silicones; an alternative assembly of the Si−O−Si unit by controlled hydrolysis of 1 is not feasible if the four valuable Si−Cl functionalities are to be retained for further derivatization. Substitution of one Cl atom per Si site of 13 gives the rac‐1,3‐disila‐2‐oxaindane rac‐15 with high selectivity.

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Selective synthesis of germasila-adamantanes through germanium–silicon shift processes

Abstract: The regioselective synthesis of germasila-adamantanes with the germanium atoms in the bridgehead positions is described starting from cyclic precursors by a cationic sila-Wagner-Meerwein (SWM) rearrangement reaction. The SWM rearrangement allows...

Cited by 5 publications

References 44 publications

Installing Quaternary Germanium Centers in Sila-Diamondoid Cores via Skeletal Isomerization

Installing Quaternary Germanium Centers in Sila-Diamondoid Cores via Skeletal Isomerization

Installing Quaternary Germanium Centers in Sila-Diamondoid Cores via Skeletal Isomerization

Adjusting the Number of Functional Groups in Vicinal Bis(trichlorosilylated) Benzenes

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