Basic Reactivity Pattern of a Cyclic Disilylated Germylene.

Małgorzata Walewska,Judith Baumgartner,Johann Hlina,Christoph Marschner,Thomas Müller

doi:10.1021/acs.organomet.6b00482

Abstract

In order to estimate the reactivity of disilylated germylene phosphine adducts, a cyclic version of this compound class was reacted with a number of different reagents. Reactions with the chalcogens sulfur, selenium, and tellurium led to dimers of the heavy ketone analogues. Reactions with water and ethyl bromide proceeded to give the respective oxidized germanol and germyl bromide. Two different reactions with alkynes were observed which led either to a germacyclopropene, by addition of tolane to the germylene, or to a silagermacyclobutene, likely formed by addition of the alkyne across a silagermene. Reaction via the silagermene was also observed in the reaction with benzophenone. Reaction of a germylene phosphine adduct with GeCl2·(dioxane) provided insertion of the silylated germylene into a Ge–Cl bond, leading to a germylated chlorogermylene phosphine adduct.

Highlights

The chemistry of higher carbene analogues is a very active field of research.1−5 Most of the studied compounds bear amino substituents, which stabilize the coordinative unsaturation of the divalent group 14 element by π-donation of the nitrogen lone pairs into its empty p orbital
In order to estimate the reactivity of disilylated germylene phosphine adducts, a cyclic version of this compound class was reacted with a number of different reagents
In the course of the last few years we have investigated the chemistry of tetrylenes with even more σ-donating oligosilanyl and germyl substituents.6−14

Summary

■ INTRODUCTION

The chemistry of higher carbene analogues (tetrylenes) is a very active field of research.− Most of the studied compounds bear amino substituents, which stabilize the coordinative unsaturation of the divalent group 14 element by π-donation of the nitrogen lone pairs into its empty p orbital. Compounds with σ-donating alkyl or aryl substituents, which lack this particular stabilization, are intrinsically more reactive and require bulky substituents to prevent di- or oligomerization.. In the course of the last few years we have investigated the chemistry of tetrylenes with even more σ-donating oligosilanyl and germyl substituents.−

■ RESULTS AND DISCUSSION

■ CONCLUSION

■ REFERENCES