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- W2009071748 abstract "Various lanthanide aryloxide complexes supported by bridged bis(amidinate) ligand L, LLnOAr(DME) (L = Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3, DME = dimethoxyethane, Ln = Y, Ar = 2,6-(Me)2C6H3 (1), 2,6-(iPr)2C6H3 (2), 2,6-(tBu)2-4-(Me)C6H2 (3); Ar = 2,6-(tBu)2-4-(Me)C6H2, Ln = Nd (4), Sm (5), Yb (6)) were synthesized, and complexes 1, 2 and 4–6 were characterized by single crystal X-ray diffraction. All the complexes are efficient precatalysts for catalytic addition of amines to carbodiimides. The catalytic activity is influenced by lanthanide metals and the aryloxide groups (Nd (4) ∼ Sm (5) < Y (3) ∼ Yb (6) and -2,6-(Me)2C6H3 < -2,6-(iPr)2C6H3 < -2,6-(tBu)2-4-(Me)C6H2). The catalytic addition reaction with 3 showed a good scope of substrates. The mechanism investigation revealed the real active intermediate being the monoguanidinate complexes supported by an aryloxide and an amidine-functionalized amidinate group, L′Ln[O2,6-(tBu)2-4-(Me)C6H2][RNCNHRN(Ar′)] (L′ = Me3SiNHC(Ph)N(CH2)3NC(Ph)NSiMe3, R = iPr, Ar′ = phenyl, Ln = Yb (8), Y (11); R = Cy, Ar′ = phenyl, Ln = Yb (10), Y (12); R = iPr, Ar′ = 4-ClC6H4, Ln = Yb (9)), which were isolated from the reactions of 6 (or 3) with amine and carbodiimide in a molar ratio of 1 : 1 : 1 and structurally characterized. The Ln-active group in the present precatalyst is a Ln–amidinate species, not the Ln–OAr group." @default.
- W2009071748 created "2016-06-24" @default.
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- W2009071748 date "2013-01-01" @default.
- W2009071748 modified "2023-09-23" @default.
- W2009071748 title "Bridged bis(amidinate) lanthanide aryloxides: syntheses, structures, and catalytic activity for addition of amines to carbodiimides" @default.
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- W2009071748 doi "https://doi.org/10.1039/c3dt33069a" @default.
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