2-Imino-2,3-dihydrobenzoxazole—a useful platform for designing rare- and alkaline earth complexes with variable di- and trianionic O,N,N, ligands

Basalov, I.V.; Kissel, A.A.; Nikolaevskaya, E.N.; Druzhkov, N.O.; Cherkasov, A.V.; Long, J.; Larionova, J.; Fukin, G.K.; Trifonov, A.A.

Авторы: Basalov Ivan V., Kissel Alexander A., Nikolaevskaya Elena N., Druzhkov Nikolai O., Cherkasov Anton V., Long Jérôme, Larionova Joulia, Fukin Georgy K., Trifonov Alexander A.
Журнал: Dalton Transactions
Год издания: 2022
Издательство: Royal Society of Chemistry
Местоположение издательства: United Kingdom
DOI: 10.1039/d1dt04139h
Аннотация: The reactions of 2-imino-2,3-dihydrobenzoxazole LH with M[N(SiMe3)2]2(THF)2 (M = Yb and Ca) and Y(CH2SiMe3)3(THF)2 proceed with the opening of the dihydrobenzoxazole ring and the elimination of HN(SiMe3)2 or SiMe4. Besides, in the case of Yb[N(SiMe3)2]2(THF)2, an electron transfer from Yb(II) to L takes place and Yb(III) complex 1 is coordinated by a dianionic phenolate ligand containing a pendant radical-anionic diazabutadiene fragment form. When LH is reacted with Ca[N(SiMe3)2]2(THF)2, C–H bond activation of a methyl fragment by imino nitrogen occurs and affords a dimeric calcium complex 2. In 2, the phenolate ligand is dianionic due to the presence of the amido-imino fragment. In situ generated ate-complex {Na(Et2O)n}{Ca[N(SiMe3)2]3} also enables C–H bond activation, however the dianionic phenolate ligand in the resulting complex 3 contains an amido-imino fragment − featuring the sequence of N–C and N[double bond, length as m-dash]C bonds opposite to that in 2. The reaction of Y(CH2SiMe3)3(THF)2 with LH affords mono(alkyl) yttrium complex 4. 4 contains a dianionic amido-imino phenolate ligand resulting from the migration of one alkyl group to the CN bond. 4 undergoes slow intramolecular C–H bond activation of the residual CH3 group to afford a yttrium complex coordinated by a trianionic diamido-phenolate ligand.
Добавил в систему: Кисель Александр Андреевич

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2-Imino-2,3-dihydrobenzoxazole—a useful platform for designing rare- and alkaline earth complexes with variable di- and trianionic O,N,N, ligandsстатья

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