Synthesis and structures of new mixed-metal lanthanide/magnesium allyl complexes

Sanchez-Barba, Luis F., Hughes, David L., Humphrey, Simon M. and Bochmann, Manfred ORCID: (2005) Synthesis and structures of new mixed-metal lanthanide/magnesium allyl complexes. Organometallics, 24 (22). pp. 5329-5334. ISSN 0276-7333

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The reaction of LnI3(THF)n (Ln = La, n = 4; Ln = Y, n = 3.5) with 3 equiv of allylMgI in THF/1,4-dioxane proceeds in moderate yields to give the unexpected mixed-metal complexes [Ln(?3-C3H5)3(µ-C4H8O2)·Mg(?1-C3H5)2(µ-C4H8O2)1.5]8 (Ln = La 1 , Y 2 ). By contrast, samarium iodide gives a salt containing a new allyl-bridged anion, [Mg(THF)6][Sm2(?3-C3H5)6(µ-?3:?3-C3H5)]2·toluene ( 3 ), while neodymium iodide affords [Mg(THF)6][Nd(?3-C3H5)4]2·2THF ( 4 ) under the same reaction conditions. On reaction with a mild proton acid such as the diketimine 2-(2,6-diisopropylphenyl)amino-4-(2,6-diisopropylphenyl)imino-2-pentene, 3 is converted into [Mg(THF)6][Sm(?3-C3H5)4]2·2THF ( 5 ), alongside Sm(?3-C3H5)2{?3-HC(MeCNC6H3iPr2-2,6)2}. The solid-state structures of 1 and 2 contain distorted trigonal-bipyramidal lanthanide centers with three ?3-allyl ligands and distorted trigonal-bipyramidal magnesium centers with two ?1-bonded allyls. Both metal centers are connected by bridging 1,4-dioxane molecules building a planar polymeric network. By contrast, 3 and 5 consist of well-defined discrete ions. Complex 3 contains an unprecedented type of binuclear anion containing two samarium centers bridged by an ?3:?3-allyl ligand, while the anion in 5 has distorted tetrahedral geometry.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Synthetic Chemistry (former - to 2017)
Faculty of Science > Research Groups > Chemistry of Light and Energy
Faculty of Science > Research Groups > Chemistry of Materials and Catalysis
Depositing User: Rachel Smith
Date Deposited: 02 Nov 2010 17:48
Last Modified: 03 Nov 2023 01:48
DOI: 10.1021/om0505155

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