Affiliation:
1. Institute of Physical Chemistry Polish Academy of Sciences Kasprzaka 44/52 01-224 Warsaw Poland
2. Faculty of Chemistry Warsaw University of Technology Noakowskiego 3 00-664 Warsaw Poland
Abstract
AbstractNitroxides find application in various areas of chemistry, and a more in‐depth understanding of factors controlling their reactivity with metal complexes is warranted to promote further developments. Here, we report on the effect of the metal centre Lewis acidity on both the distribution of the O‐ and N‐centered spin density in 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) and turning TEMPO from the O‐ to N‐radical mode scavenger in metal‐TEMPO systems. We use Et(Cl)Zn/TEMPO model reaction system with tuneable reactivity in the solid state and solution. Among various products, a unique Lewis acid‐base adduct of Cl2Zn with the N‐ethylated TEMPO was isolated and structurally characterised, and the so‐called solid‐state ′slow chemistry′ reaction led to a higher yield of the N‐alkylated product. The revealed structure‐activity/selectivity correlations are exceptional yet are entirely rationalised by the mechanistic underpinning supported by theoretical calculations of studied model systems. This work lays a foundation and mechanistic blueprint for future metal/nitroxide systems exploration.
Funder
Narodowe Centrum Nauki
Horizon 2020 Framework Programme
Narodowe Centrum Badań i Rozwoju
Interdyscyplinarne Centrum Modelowania Matematycznego i Komputerowego UW
Cited by
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