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Triphenylantimony(V) o ‐amidophenolates with unsymmetrical N ‐aryl group for a reversible dioxygen binding
Author(s) -
Poddel'sky Andrey I.,
Kurskii Yury A.,
Piskunov Alexandr V.,
Somov Nikolay V.,
Cherkasov Vladimir K.,
Abakumov Gleb A.
Publication year - 2011
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.1738
Subject(s) - chemistry , isopropyl , steric effects , aryl , stereochemistry , alkyl , molecule , peroxide , medicinal chemistry , organic chemistry
New triphenylantimony(V) o ‐amidophenolates (AP‐Me,Et)SbPh 3 (1) and (AP‐Me,iPr)SbPh 3 (2) with unsymmetrically substituted N ‐aryl groups and (AP‐Et,Et)SbPh 3 (3) with symmetrical N ‐aryl group {AP‐R 1 ,R 2 is 4,6‐di‐ tert ‐butyl‐ N ‐[2‐alkyl(R 1 ),6‐alkyl(R 2 )‐phenyl]‐ o ‐amidophenolate dianion} were synthesized and characterized in detail. Complexes were examined for dioxygen activity. The unsymmetrical complexes 1 and 2 were found to form different geometrical isomers (A and B) of spiroendoperoxides [L‐R 1 ,R 2 (O 2 )]SbPh 3 (4 and 5, respectively) with different dispositions of peroxide group and N ‐aryl fragment (methyl and peroxide group are on the same side of the molecule in the less shielded isomer A, and on different sides in the more hindered isomer B). The isomer A prevails over isomer B, reflecting the possibility of steric control on the dioxygen‐binding reaction. Complex 3, where R 1 = R 2 = Et, formed the isomers 6A and 6B as 50:50. The ratio 4A:4B was 60:40 (for methyl‐ethyl containing complex 4) and it increased up to 80:20 for methyl‐isopropyl‐containing 5. The molecular structure of isomers 4A and 4B was confirmed by X‐ray analysis. Copyright © 2010 John Wiley & Sons, Ltd.