Synthesis, Structure, and Reactivity of Lanthanide Complexes Incorporating Indolyl Ligands in Novel Hapticities
Authors:
- 26 July 2013
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 52 (16) , 9549-9556
Abstract
The chemistry of interactions of 2-(2,6-diisopropylphenylaminomethylene)indole ligand (1) with europium and ytterbium amides is described. Reaction of 2-(2,6-diisopropylphenylaminomethylene)indole 2-(2,6-i-Pr2C6H3NHCH2)C8H5NH (1) with europium amide [(Me3Si)2N]3EuIII(μ-Cl)Li(THF)3 afforded a novel europium(II) complex formulated as {[μ-η6:η1:η1-2-(2,6-i-Pr2C6H3N═CH)C8H5N]Eu[2-(2,6-i-Pr2C6H3N═CH)C8H5N]}2 (2), having a bridged indolyl ligand in the novel μ-η6:η1:η1 hapticities with the reduction of europium(III) to europium(II) and the oxidation of amino to imino group. Reaction of 2-(2,6-diisopropylphenylaminomethylene)indole 2-(2,6-i-Pr2C6H3NHCH2)C8H5NH (1) with ytterbium(III) amide [(Me3Si)2N]3YbIII(μ-Cl)Li(THF)3 produced the only deprotonated ytterbium(III) complex formulated as [2-(2,6-i-Pr2C6H3NCH2)C8H5N]Yb[N(SiMe3)2](THF)2 (3), having an η1 hapticity indolyl ligand. Reaction of 2 with formamidine [(2,6-Me2C6H3)NCHNH(C6H3Me2-2,6)] produced {[μ-η3:η1:η1-2-(2,6-i-Pr2C6H3N═CH)C8H5N]Eu[(2,6-Me2C6H3)NCHN(C6H3Me2-2,6)](THF)}2 (4), which has a bridged indolyl ligand in the novel μ-η3:η1:η1 hapticities, whereas the reaction of 2 with the more sterically bulky formamidine [(2,6-i-Pr2C6H3)NCHNH(C6H3i-Pr2-2,6)] afforded complex {[μ-η2:η1:η1-2-(2,6-i-Pr2C6H3N═CH)C8H5N]Eu[(2,6-i-Pr2C6H3)N═CHN(C6H3i-Pr2-2,6)](THF)}2 (5), having the indolyl ligand in the novel μ-η2:η1:η1 hapticities. The results represent the first example of organometallic complexes having indolyl ligands in the novel μ-η6:η1:η1, μ-η3:η1:η1, and μ-η2:η1:η1 bonding modes with metal.Keywords
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