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σ-Bonded organometallic derivatives of yttrium(III) and thulium(III): An unusual ligand coupling reaction mediated by thulium(III)

Lookup NU author(s): Dr Keith Izod, Emeritus Professor Bill CleggORCiD, Dr Ross Harrington


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The reaction between LnI3(THF)3.5 and 2 equiv. of {(Me3Si)2(Me2MeOSi)C}K (1) in THF at room temperature yields only the mono-substituted products {(Me3Si)2(Me2MeOSi)C}LnI2(THF)2 [Ln = Y (5), Tm (6)]; under more forcing conditions decomposition occurs. In contrast, the metathesis reaction between TmI3(THF)3.5 and 2 equiv. of the lithium iodide-containing salt {(Me3Si)2(Me2MeOSi)C}K(LiI)x yields the highly unusual separated ion pair complex [[{(Me3Si)2C(SiMe2)}2O]TmI2{Li(THF)3}2][[{(Me3Si)2C(SiMe2)}2O]TmI2] (8). The dianionic ligand in 8 is derived from the coupling of 2 equiv. of (Me3Si)2(Me2MeOSi)C-, accompanied by the formal elimination of Me2O. The structures of compounds 5, 6, and 8 have been determined by X-ray crystallography; compound 8 crystallizes as an unusual ion pair, the cation and anion of which differ only in the inclusion of 2 equiv. of Li(THF)3 in the former, bridged to thulium by iodide ions. © 2006 Elsevier B.V. All rights reserved.

Publication metadata

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

Publication type: Article

Publication status: Published

Journal: Journal of Organometallic Chemistry

Year: 2007

Volume: 692

Issue: 4

Pages: 806-812

ISSN (print): 0022-328X

ISSN (electronic): 1872-8561

Publisher: Elsevier


DOI: 10.1016/j.jorganchem.2006.10.017


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