Isolable Geminal Bisgermenolates: A New Synthon in Organometallic Chemistry

Angew Chem Weinheim Bergstr Ger. 2021 Oct 25;133(44):23838-23842. doi: 10.1002/ange.202111636. Epub 2021 Sep 28.

Abstract

We have synthesized the first isolable geminal bisenolates L2K2Ge[(CO)R]2 (R=2,4,6-trimethylphenyl (2 a,b), L=THF for (2 a) or [18]-crown-6 for (2 b)), a new synthon for the synthesis of organometallic reagents. The formation of these derivatives was confirmed by NMR spectroscopy and X-ray crystallographic analysis. The UV/Vis spectra of these anions show three distinct bands, which were assigned by DFT calculations. The efficiency of 2 a,b to serve as new building block in macromolecular chemistry is demonstrated by the reactions with two different types of electrophiles (acid chlorides and alkyl halides). In all cases the salt metathesis reaction gave rise to novel Ge-based photoinitiators in good yields.

A convenient method to obtain geminal bisenolates L2K2Ge[(CO)R]2 (R=2,4,6‐trimethylphenyl (1 a,b), L=THF for (1 a) or [18]‐crown‐6 for (1 b)), a new synthon for the synthesis of organometallic reagents, is reported. Selected examples of electrophiles were used to display the efficiency of 1 a,b as new building blocks in organometallic chemistry.

Keywords: SET reaction; acylgermanes; bisenolates; germenolates; photoinitiators.