Crown-hydroxylamines are pH-dependent chelating N,O-ligands with a potential for aerobic oxidation catalysis

Crown-hydroxylamines are pH-dependent chelating N,O-ligands with a potential for aerobic oxidation catalysis Full article

Journal

Nature Communications
ISSN: 2041-1723

Output data

Year: 2023, Volume: 14, Number: 1, Article number : 7673, Pages count : DOI: 10.1038/s41467-023-43530-6

Authors

Lesnikov Vladislav K. ¹ , Golovanov Ivan S. ¹ , Nelyubina Yulia V. ² , Aksenova Svetlana A. ² , Sukhorukov Alexey Yu. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991, Leninsky prospect, 47, Moscow, Russian Federation
2	A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991, Vavilova str. 28, Moscow, Russian Federation

Despite the rich coordination chemistry, hydroxylamines are rarely used as ligands for transition metal coordination compounds. This is partially because of the instability of these complexes that undergo decomposition, disproportionation and oxidation processes involving the hydroxylamine motif. Here, we design macrocyclic poly-N-hydroxylamines (crown-hydroxylamines) that form complexes containing a d-metal ion (Cu(II), Ni(II), Mn(II), and Zn(II)) coordinated by multiple (up to six) hydroxylamine fragments. The stability of these complexes is likely to be due to a macrocycle effect and strong intramolecular H-bonding interactions between the N−OH groups. Crown-hydroxylamine complexes exhibit interesting pH-dependent behavior where the efficiency of metal binding increases upon deprotonation of the hydroxylamine groups. Copper complexes exhibit catalytic activity in aerobic oxidation reactions under ambient conditions, whereas the corresponding complexes with macrocyclic polyamines show poor or no activity. Our results show that crown-hydroxylamines display anomalous structural features and chemical behavior with respect to both organic hydroxylamines and polyaza-crowns.

Lesnikov V.K. , Golovanov I.S. , Nelyubina Y.V. , Aksenova S.A. , Sukhorukov A.Y.
Crown-hydroxylamines are pH-dependent chelating N,O-ligands with a potential for aerobic oxidation catalysis
Nature Communications. 2023. V.14. N1. 7673 . DOI: 10.1038/s41467-023-43530-6 WOS Scopus OpenAlex

Web of science:	WOS:001110180200012
Scopus:	2-s2.0-85178304739
OpenAlex:	W4388936313

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OpenAlex	13
Scopus	11
Web of science	12