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

被引:38
作者
Sánchez-Barba, LF
Hughes, DL
Humphrey, SM
Bochmann, M [1 ]
机构
[1] Univ E Anglia, Sch Chem Sci & Pharm, Wolfson Mat & Catalylsis Ctr, Norwich NR4 7TJ, Norfolk, England
[2] Univ Cambridge, Univ Chem Lab, Cambridge CB2 1EW, England
基金
英国工程与自然科学研究理事会;
关键词
D O I
10.1021/om0505155
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction of LnI(3)(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(eta(3)-C3H5)(3)(mu-C4H8O2)center dot Mg(eta(1)-C3H5)(2)(mu-C4H8O2)1.5](infinity) (Ln = La 1, Y 2). By contrast, samarium iodide gives a salt containing a new allyl-bridged anion, [Mg(THF)(6)] [Sm-2(eta(3)-C3H5)(6)(mu-eta(3):eta(3)- C3H5)](2)center dot toluene (3), while neodymium iodide affords [Mg(THF)(6)][Nd(eta(3)-C3H5)(4)](2)center dot 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(eta(3)-C3H5)(4)](2)center dot 2THF (5), alongside SM(eta(3)-C3H5)(2){kappa(3)-HC((MeCNC6H3Pr2)-Pr-i-2,6)(2)}. The solid-state structures of 1 and 2 contain distorted trigonal-bipyramidal lanthanide centers with three eta(3)-allyl ligands and distorted trigonal-bipyramidal magnesium centers with two eta(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 eta(3):eta(3)-allyl ligand, while the anion in 5 has distorted tetrahedral geometry.
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页码:5329 / 5334
页数:6
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