959422-05-0Relevant articles and documents
Reduction of carbodiimides by samarium(II) bis(trimethylsilyl)amides - Formation of oxalamidinates and amidinates through C-C coupling or C-H activation
Deacon, Glen B.,Forsyth, Craig M.,Junk, Peter C.,Wang, Jun
, p. 10022 - 10030 (2007)
The reaction of [Sm{N(SiMe3)2}2(THF) 2] (THF = tetrahydrofuran) with carbodiimides RN=C=NR (R = Cy, C 6H3-2,6-iPr2) led to the formation of dinuclear SmIII complexes via differing C-C coupling processes. For R = Cy, the product [{(Me3Si)2N}2Sm(μ- C2N4Cy4)Sm{N(SiMe3) 2}2] (1) has an oxalamidinate [C2N 4Cy4]2- ligand resulting from coupling at the central C atoms of two CyNCNCy moieties. In contrast, for R = C 6H3-2,6-iPr2, H transfer and an unusual coupling of two iPr methine C atoms resulted in a linked formamidinate complex, [{(Me3Si)2N}2Sm{μ- (RNC(H)N(Ar-Ar)NC(H)NR)}Sm{N(SiMe3)2}2] (2) (Ar-Ar = C6H3-2-iPr-6-C(CH3) 2C(CH3)2-6′-C6H 3-2′-iPr). Analogous reactions of RN=C=NR (R = Cy, C6H3-2,6-iPr2) with the Sm II "ate" complex [Sm{N(SiMe2)3Na] gave 1 for R = Cy, but a novel C-substituted amidinate complex, [(THF)Na{N(R)C(NR)CH2Si(Me2)N(SiMe3)} Sm{N(SiMe3)2}2] (3), for R = C 6H3-2,6-iPr2, via γ C-H activation of a N(SiMe3)2 ligand.
