# Bonding and Reactivity of Germanium Enolates toward Group 14 Halides

## TL;DR

This study explores how germanium enolates react with group 14 halides to form new acylgermanes with unique bonding and light-absorbing properties.

## Contribution

The paper introduces new reactivity patterns of triacyl- and bisgermenolates under mechanochemical conditions, leading to novel acylgermane structures.

## Key findings

- Reactions with halosilanes produced silyl-substituted acylgermanes.
- Chlorogermanes and chlorostannanes yielded Ge–Ge and Ge–Sn bonded acylgermanes.
- Bisgermenolates formed unprecedented four-membered Ge–Ge and Ge–Sn ring systems.

## Abstract

We report the reactivity of triacylgermenolate (1)
and geminal bisgermenolate (13) toward group 14 halides
under mechanochemical conditions, enabling efficient access to novel
acylgermanes. Reactions with halosilanes afforded a series of silyl-substituted
acylgermanes (3–7), while treatment
with chlorogermanes and chlorostannanes yielded Ge–Ge and Ge–Sn
bonded acylgermanes (8–11). In contrast,
the bisgermenolate displayed divergent reactivity, forming unprecedented
four-membered Ge–Ge and Ge–Sn ring systems (15, 16). UV–Vis spectroscopy revealed pronounced
bathochromic shifts and enhanced absorption for the heavier congeners,
with photo-CIDNP experiments confirming α-cleavage and radical
generation from the cyclic Ge–Ge compound. Overall, these findings
establish triacyl- and bisgermenolates as versatile building blocks
for accessing novel acylgermanes with tunable bonding motifs and photochemical
properties.