Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance work on Wednesday 27th March 2019 from 11:00 AM to 1:00 PM (GMT).

During this time our website performance may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 14, 2015
Previous Article Next Article

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

Author affiliations

Abstract

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 09 Jan 2015, accepted on 04 Mar 2015 and first published on 11 Mar 2015


Article type: Paper
DOI: 10.1039/C5DT00095E
Citation: Dalton Trans., 2015,44, 6630-6637

  •   Request permissions

    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

Search articles by author

Spotlight

Advertisements