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Amidation of zirconium tetrachloride with dimethylamidolithium; tetrakis(dimethylamido)zirconium

SyntheticPage 113
DOI: 10.1039/SP113
Submitted Aug 21, 2001, published Aug 21, 2001
Colin Morton (c.morton@warwick.ac.uk)
A contribution from Scott group, Warwick University


			Reaction Scheme: Amidation of zirconium tetrachloride with dimethylamidolithium

Chemicals Used

toluene (distilled from sodium)
lithium dimethylamide (Aldrich) See also synthesis
zirconium tetrachloride (Aldrich)

Procedure

Toluene (80 ml) was added to a mixture of [Li(NMe2)] (3.7 g, 0.068 mol) and ZrCl4 (4.0 g, 0.017 mol) at room temperature. After stirring overnight, the solvent was removed in vacuo and the yellow residue was sublimed at 80°C and 10-3 mbar giving an off-white crystalline solid. Yield = 83%, 3.7g.

Author's Comments

Standard schlenk line procedures are used. The sublimation was carried out using schlenk-line vacuum. We have carried out this procedure many times.

Data

1H NMR (293 K, d6-benzene) 3.05 (s, 24H, NMe2).

Lead Reference

D. C. Bradley and I. M. Thomas, J. Chem. Soc., 1960, 3857.

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Keywords: 113, amido, organometallic starting materials, zirconium

Post new comment
  • Registered user Edward CrustAug 22 2001 2:25PM

    When adding the toluene to the amide, it can help to keep the mixture cool (acetone/dry ice) until there is sufficient solvent to move all of the solid. Otherwise a lot of heat can be generated causing a blackening of the solution.

  • Registered user Colin MortonAug 24 2001 9:45AM

    Zirconium tetrachloride is used as supplied from Aldrich.

  • Registered user Peter ScottMar 20 2010 11:15AM

    This compound is no longer comercially available, and in fact recently we have found that the commercial material has been of poorer quality thus reducing the yield of zirconium amide. We have however recently synthesised LiNMe2 from lithium butyl and dimethylamine (gas). This prep needs to be conducted with care and our first attempt was troubled with stirring problems, but we did isolate a excellent yield of pure white LiNMe2 - the commercial material was grey and getting greyer! My group will report this prep soon.

    • Registered user Peter ScottJun 9 2010 7:03PM

      The synthesis is now published and a link has been added in "Chemicals Used" above

  • Guest Soumen MukherjeeJun 11 2014 8:58AMInsitu prep

    Hi! Can I do an insitu preparation of tetrakis(dimethylamido)zirconium? What we plan is to make LiNMe2 in Toluene(same process but use Toluene instead of pentane as mentioned) and in the same suspension add ZrCl4 at low temperature, without isolating the LiNMe2. Regards, Soumen

    • Registered user Peter ScottJun 11 2014 11:08AM

      Not sure what you mean by "can I do". You can do it, but it is very unlikely to work so well. The sublimation will probably produce oily material alongside the amide which will then fail to crystallise. If you go ahead with this I would suggest you use an excess of the amine so that all the BuLi is used up, then evaporate to remove the excess amine. We published a detailed prep of LiNMe2 so that you do not have to cut corners like this. You need to do a full and complete risk assessment.

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