Linear and Bent Cp*2 Si: Reversible Phase Transition of a Key Molecule

Angew Chem Int Ed Engl. 2023 May 15;62(21):e202301609. doi: 10.1002/anie.202301609. Epub 2023 Apr 17.

Abstract

The solid-state structure of decamethylsilicocene Cp*2 Si with a bent and a linear molecule in the same unit cell was so far considered an exception in relation to the structures of its all-bent heavier analogues Cp*2 E with E=Ge, Sn, Pb. Here, we present the solution to this conundrum by reporting a low-temperature phase, where all three symmetrically independent molecules are present in a bent formation. This reversible enantiotropic phase transition occurs in the temperature range between 80 K and 130 K and provides a rationale for the unexpected linear molecule based in entropy beyond hand-waving explanations such as electronic reasons or packing effects.

Keywords: Main Group Chemistry; Phase Transition; Silicocene; Silicon; Structural Chemistry.