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Synthesis of Intramolecular P/Al‐Based Frustrated Lewis Pairs via Aluminum‐Tin‐Exchange and their Reactivity toward CO 2
Author(s) -
Federmann Patrick,
Müller Robert,
Beckmann Fabian,
Lau Caroline,
Cula Beatrice,
Kaupp Martin,
Limberg Christian
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202200404
Subject(s) - chemistry , reactivity (psychology) , frustrated lewis pair , tin , intramolecular force , atom (system on chip) , derivative (finance) , linker , aluminium , stereochemistry , medicinal chemistry , computational chemistry , lewis acids and bases , catalysis , organic chemistry , medicine , alternative medicine , pathology , computer science , financial economics , economics , embedded system , operating system
Frustrated Lewis pairs (FLPs) composed of acidic alane and basic phosphane functions, separated by a xanthene linker, can be prepared through the corresponding Me 3 Sn derivative and methyl aluminum compounds with elimination of Me 4 Sn. This way MeClAl‐, Cl 2 Al‐ and (C 6 F 5 ) 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 CO 2 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 CO 2 capture occurs at higher pressure and under ambient conditions CO 2 is released again, while for Cl 2 Al and (C 6 F 5 ) 2 Al CO 2 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 (C 6 F 5 ) 2 Al further stabilization is achieved through a low reorganization energy.