C-ON bond homolysis of alkoxyamines triggered by paramagnetic copper(II) salts

C-ON bond homolysis of alkoxyamines triggered by paramagnetic copper(II) salts Full article

Journal

Inorganic Chemistry Frontiers
ISSN: 2052-1553

Output data

Year: 2016, Volume: 3, Number: 11, Pages: 1464-1472 Pages count : 9 DOI: 10.1039/c6qi00277c

Authors

Audran Gerard ¹ , Bagryanskaya Elena ² , Bagryanskaya Irina ² , Bremond Paul ¹ , Edeleva Mariya ² , Marque Sylvain R.A. ^1,2 , Parkhomenko Dmitriy ² , Tretyakov Evgeny ² , Zhivetyeva Svetlana ²

Affiliations

1	(Данные Web of science) Aix Marseille Univ, UMR 7273, ICR, CNRS, Case 551,Ave Escadrille Normandie Niemen, F-13397 Marseille 20, France
2	(Данные Web of science) NN Vorozhtsov Novosibirsk Inst Organ Chem SB RAS, Pr Lavrentjeva 9, Novosibirsk 630090, Russia

The metal complexation reactions of bis(hexafluoroacetylacetonato)copper(II)(Cu(hfac)(2)) with alkoxyamines (diethyl(2,2-dimethyl-1-(tert-butyl-(1-(pyridine-4-yl)ethoxy)amino)propyl)phosphonate and diethyl (2,2-dimethyl-1-(tert-butyl-(1-(pyridine-2-yl)ethoxy)amino)propyl)phosphonate) were studied. According to X-ray analysis, the molecular and crystal structures of 1:1 complexes depend on the configuration of the free alkoxyamines, that is dimeric (RSSR) and chain-polymeric (RR/SS) structures for para-pyridyl-substituted alkoxyamines, and cyclic unimeric (RS/SR) structure for ortho-pyridyl derivative. The complex (2:1 ratio Cu(hfac)(2)/alkoxyamine) for ortho-pyridyl-substituted alkoxyamine is not resolved. Upon warming, ortho complexes decomposed into free alkoxyamines and only a weak activation was observed. Upon warming, para complexes decomposed into their corresponding unimers, and then, a 21-fold increase in the rate constant of the C-ON bond homolysis was observed compared to the corresponding free alkoxyamines. Tuning of the homolysis rate constant of the C-ON bond via addition of pyridine is also reported.

Audran G. , Bagryanskaya E. , Bagryanskaya I. , Bremond P. , Edeleva M. , Marque S.R.A. , Parkhomenko D. , Tretyakov E. , Zhivetyeva S.
C-ON bond homolysis of alkoxyamines triggered by paramagnetic copper(II) salts

Inorganic Chemistry Frontiers. 2016. V.3. N11. P.1464-1472. DOI: 10.1039/c6qi00277c WOS Scopus РИНЦ

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