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Deacon GB, Forsyth CM, Junk PC, et al. Reduction of carbodiimides by samarium(II) bis(trimethylsilyl)amides-formation of oxalamidinates and amidinates through C-C coupling or C-H activation. Inorg Chem. 2007;46(23):10022-30doi: 10.1021/ic701497c.
Deacon, G. B., Forsyth, C. M., Junk, P. C., & Wang, J. (2007). Reduction of carbodiimides by samarium(II) bis(trimethylsilyl)amides-formation of oxalamidinates and amidinates through C-C coupling or C-H activation. Inorganic chemistry, 46(23), 10022-30. https://doi.org/10.1021/ic701497c
Deacon, Glen B, et al. "Reduction of carbodiimides by samarium(II) bis(trimethylsilyl)amides-formation of oxalamidinates and amidinates through C-C coupling or C-H activation." Inorganic chemistry vol. 46,23 (2007): 10022-30. doi: https://doi.org/10.1021/ic701497c
Deacon GB, Forsyth CM, Junk PC, Wang J. Reduction of carbodiimides by samarium(II) bis(trimethylsilyl)amides-formation of oxalamidinates and amidinates through C-C coupling or C-H activation. Inorg Chem. 2007 Nov 12;46(23):10022-30. doi: 10.1021/ic701497c. Epub 2007 Oct 11. PMID: 17929807.
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Inorg Chem. 2007 Nov 12;46(23):10022-30. doi: 10.1021/ic701497c. Epub 2007 Oct 11.

Reduction of carbodiimides by samarium(II) bis(trimethylsilyl)amides-formation of oxalamidinates and amidinates through C-C coupling or C-H activation.

Inorganic chemistry

Glen B Deacon, Craig M Forsyth, Peter C Junk, Jun Wang

Affiliations

  1. School of Chemistry, Monash University, P.O. Box 23, Victoria, 3800 Australia.

PMID: 17929807 DOI: 10.1021/ic701497c

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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