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Synthesis and structures of Ln(II) and Ln(III) dialkyls derived from LnI2 (Ln = Nd, Tm, Yb)

Lookup NU author(s): Dr Keith Izod, Professor William Clegg, Dr Ross Harrington

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Abstract

Whereas the reactions between either NdI2 or TmI2 and 1 equiv of the dipotassium salt [{(Me3Si)2C-(SiMe 2)}2O]K2(OEt2) (2) yield only intractable mixtures of products, reactions between LnI2 and 1 equiv of {(Me3Si)(Me2MeOSi)C(SiMe2CH 2)}2K2 (3) yield the lanthanide(III) compounds {(Me3Si)(Me2-MeOSi)C(SiMe2CH2)} 2Ln(OMe)(THF) [Ln = Tm (9), Nd (10)] via a ligand degradation reaction. In contrast, YbI2 reacts smoothly with either 2 or 3 to give the ytterbium(II) alkyls [{(Me3Si)2C(SiMe 2)}2O]-Yb(THF)2 (4) and {(Me 3Si)(Me2MeOSi)C(SiMe2CH2)} 2Yb(THF) (5), respectively, in excellent yields. Compounds 4 and 5 have been characterized by multielement (1H, 13C{ 1H}, 29Si, and 171Yb) NMR spectroscopy, and compounds 4, 5, 9, and 10 by elemental analyses and X-ray crystallography. Compounds 9 and 10 crystallize as structurally similar monomers with a distorted trigonal prismatic geometry about the Ln(III) ions; in 4 and 5 the Yb centers lie in a distorted trigonal bipyramidal geometry. Compound 5, although potentially diastereomeric, gives rise to a single set of NMR signals over the temperature range 20 to -80°C, suggesting either the presence of only one diastereomer or that exchange between diastereomers is rapid on the NMR time scale. © 2007 American Chemical Society.

Publication metadata

Author(s): Bowman LJ, Izod K, Clegg W, Harrington RW

Publication type: Article

Publication status: Published

Journal: Organometallics

Year: 2007

Volume: 26

Issue: 10

Pages: 2646-2651

ISSN (print): 0276-7333

ISSN (electronic): 1520-6041

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/om0611711

DOI: 10.1021/om0611711

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