Reduction of carbodiimides by samarium(II) bis(trimethylsilyl)amides-formation of oxalamidinates and amidinates through C-C coupling or C-H activation |
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Authors: | Deacon Glen B Forsyth Craig M Junk Peter C Wang Jun |
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Institution: | School of Chemistry, Monash University, P.O. Box 23, Victoria, 3800 Australia. |
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Abstract: | The reaction of Sm{N(SiMe3)2}2(THF)2] (THF=tetrahydrofuran) with carbodiimides RN=C=NR (R=Cy, C6H3-2,6-iPr2) led to the formation of dinuclear SmIII complexes via differing C-C coupling processes. For R=Cy, the product {(Me3Si)2N}2Sm(micro-C2N4Cy4)Sm{N(SiMe3)2}2] (1) has an oxalamidinate C2N4Cy4]2- ligand resulting from coupling at the central C atoms of two CyNCNCy moieties. In contrast, for R=C6H3-2,6-iPr2, H transfer and an unusual coupling of two iPr methine C atoms resulted in a linked formamidinate complex, {(Me3Si)2N}2Sm{micro-(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'-C6H3-2'-iPr). Analogous reactions of RN=C=NR (R=Cy, C6H3-2,6-iPr2) with the SmII "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=C6H3-2,6-iPr2, via gamma C-H activation of a N(SiMe3)2 ligand. |
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