Synthesis of Intramolecular P/Al-Based Frustrated Lewis Pairs via Aluminum-Tin-Exchange and their Reactivity toward CO₂.

ABSTRACT: Frustrated Lewis pairs (FLPs) composed of acidic alane and basic phosphane functions, separated by a xanthene linker, can be prepared through the corresponding Me₃ Sn derivative and methyl aluminum compounds with elimination of Me₄ Sn. This way MeClAl-, Cl₂ Al- and (C₆ F₅ )₂ Al- moieties could be introduced and the resulting FLPs are stabilized by a further equivalent of the alane precursors. In contact with the FLPs CO₂ is bound via the C atom at the phosphane functions and the two O atoms at the Al centers. The residues at the latter determine the binding strength. Hence, in case of MeClAl CO₂ capture occurs at higher pressure and under ambient conditions CO₂ is released again, while for Cl₂ Al and (C₆ F₅ )₂ Al CO₂ binding becomes irreversible. The results of DFT calculations rationalize these findings by the high thermodynamic stabilization in case of more electronegative residues, which concomitantly lead to higher barriers, and in case of (C₆ F₅ )₂ Al further stabilization is achieved through a low reorganization energy.

SUBMITTER: Federmann P 

PROVIDER: S-EPMC9314872 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature