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Issue 29, 2010
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Steric control of the reduction of carbodiimides by samarium(ii) and the synthesis of very crowded samarium(iii) complexes

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Abstract

Reduction of N,N′-di(2,6-diisopropylphenyl)carbodiimide (DippNCNDipp) by [SmL2(thf)2] (1) (L = N,N′-bis(2,6-diisopropylphenyl)formamidinate, DippNC(H)NDipp) in PhMe gave [Sm(L)3] (2) in good yield. An analogous reaction of 1 with N,N′-dimesitylcarbodiimide (MesNCNMes) gave [SmL2(MesNC(H)NMes)] (3). In contrast, reduction of N,N′-dicyclohexylcarbodiimide (CyNCNCy) by 1 in PhMe gave mixture of products from which [SmL2(CyNC(CH2Ph)NCy)] (4) and [SmL2(CyNC(H)NCy)] (5) were isolated by fractional crystallisation. Using thf as the reaction solvent, solely compound 5 was crystallised. Reactions of [Sm(L)2(C[triple bond, length as m-dash]CPh)(thf)] (6) with the carbodiimides RNCNR (R = Cy, Mes) gave [Sm(L)2(RNC(C[triple bond, length as m-dash]CPh)NR)] (R = Cy (7) or Mes (8)) which are analogues of 4. No reaction was observed between 6 and DippNCNDipp.

Graphical abstract: Steric control of the reduction of carbodiimides by samarium(ii) and the synthesis of very crowded samarium(iii) complexes

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Article information


Submitted
21 Oct 2009
Accepted
14 Dec 2009
First published
20 Jan 2010

Dalton Trans., 2010,39, 6732-6738
Article type
Paper

Steric control of the reduction of carbodiimides by samarium(II) and the synthesis of very crowded samarium(III) complexes

M. L. Cole, G. B. Deacon, C. M. Forsyth, P. C. Junk, D. Polo-Cerón and J. Wang, Dalton Trans., 2010, 39, 6732 DOI: 10.1039/B922031C

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