Autor: |
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. |
Předmět: |
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Zdroj: |
Dalton Transactions: An International Journal of Inorganic Chemistry; 2/7/2022, Vol. 51 Issue 5, p1995-2004, 10p |
Abstrakt: |
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 [R–N=C(CH3)–C(=CH2)–NR′]− (R = 2,4-tBu2-C6H2O; R′ = 2,6-iPr2C6H3). 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 [R–N–C(=CH2)–C(CH3)=NR′]− featuring the sequence of N–C and N=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 C=N bond [R–N–C(Me)(CH2SiMe3)–C(Me)=NR′]. 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 [R–N–C(Me)(CH2SiMe3)–C(=CH2)NR′]. [ABSTRACT FROM AUTHOR] |
Databáze: |
Complementary Index |
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