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Issue 14, 2015
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Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η15-O(CH2)2C2B9H9]Ln(σ:η1-CH2C6H4-o-NMe2)(THF)2

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Rare-earth metallacarborane alkyls can be stabilized by the incorporation of a functional sidearm into both π and σ ligands. Reaction of [Me3NH][7,8-O(CH2)2-7,8-C2B9H10] with one equiv. of Ln(CH2C6H4-o-NMe2)3 gave metallacarborane alkyls [η15-O(CH2)2C2B9H9]Ln(σ:η1-CH2C6H4-o-NMe2)(THF)2 (Ln = Y (3a), Gd (3b), Er (3c)) via alkane elimination. They represent the first examples of rare-earth metallacarborane alkyls. Treatment of 3a with RN[double bond, length as m-dash]C[double bond, length as m-dash]NR (R = Cy, iPr) or 2-benzoylpyridine afforded the corresponding mono-insertion products [η15-O(CH2)2C2B9H9]Y[η2-(RN)2C(CH2C6H4-o-NMe2)](DME) (R = Cy (4a), iPr (5a)) or [η15-O(CH2)2C2B9H9]Y[C5H4NC(Ph)(CH2C6H4-o-NMe2)O](THF)2 (6a), respectively. Complex 3a also reacted with ArNCO or ArNC (Ar = 2,6-diisopropylphenyl, 2,6-dimethylphenyl) to give di-insertion products [η15-O(CH2)2C2B9H9]Y[OC([double bond, length as m-dash]NC6H3Me2)N(C6H3Me2)C(CH2C6H4-o-NMe2)O](THF)2 (7a) or [η15-O(CH2)2C2B9H9]Y[C([double bond, length as m-dash]NC6H3iPr2)C([double bond, length as m-dash]NC6H3iPr2)(CH2C6H4-o-NMe2)](DME) (8a). These results showed that the reactivity pattern of the Ln–C σ bond in rare-earth metallacarborane alkyls was dependent on the nature of the unsaturated organic molecules. New complexes were characterized by various spectroscopic techniques and elemental analysis. Some were further confirmed by single-crystal X-ray analysis.

Graphical abstract: Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η1:η5-O(CH2)2C2B9H9]Ln(σ:η1-CH2C6H4-o-NMe2)(THF)2

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Supplementary files

Article information

09 Jan 2015
04 Mar 2015
First published
11 Mar 2015

Dalton Trans., 2015,44, 6630-6637
Article type

Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η15-O(CH2)2C2B9H9]Ln(σ:η1-CH2C6H4-o-NMe2)(THF)2

J. Yang and Z. Xie, Dalton Trans., 2015, 44, 6630
DOI: 10.1039/C5DT00095E

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