Synthesis and structural elucidation of alkyl, amido, and mixed. alkyl-amido "highly-coordinated" zincates

Armstrong, D.R. and Dougan, C. and Graham, D.V. and Hevia, E. and Kennedy, A.R. (2008) Synthesis and structural elucidation of alkyl, amido, and mixed. alkyl-amido "highly-coordinated" zincates. Organometallics, 27 (23). pp. 6063-6070. ISSN 0276-7333 (http://dx.doi.org/10.1021/om800786n)

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Abstract

The solution and solid-state characterization of the tetraorganozincates [(TMEDA)2Li2ZnMe(NMe2)3] (2) and [(TMEDA)2Li2ZnMe4] (4) and the all-amido triorganozincate [{(TMEDA)LiZn(NMe2)3}2] (3) are reported. X-ray crystallographic studies reveal that 2 and 4 exhibit similar structural motifs, namely trinuclear Li···Zn···Li chain arrangements held together by a methyl and three amido ligands in the former and exclusively by methyl groups in the latter, whereas 3 adopts a longer tetranuclear Li···Zn···Zn···Li chain arrangement with all NMe2 ligands. The zinc coordination in all these structures is distorted tetrahedral. DFT calculations revealed that the formation of tetraorganozincate 4 by cocomplexation of 2 equiv of MeLi and Me2Zn is thermodynamically preferred over the parent triorganozincate [(TMEDA)LiZnMe3]. Preliminary studies show that the tris(amido)alkyl zincate 2 is a poor Brønsted base for metalation (zincation) of functionalized aromatic substrates such as anisole, N,N-diisopropylbenzamide, and benzonitrile.

ORCID iDs

Armstrong, D.R., Dougan, C., Graham, D.V., Hevia, E. ORCID logoORCID: https://orcid.org/0000-0002-3998-7506 and Kennedy, A.R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015;
  • Item type:Article
    ID code:17013
    Dates:
    Date
    Event
    8 December 2008
    Published
    Notes:http://suprimo.lib.strath.ac.uk/primo_library/libweb/action/display.do?ct=display&doc=SUSFX954925505259&indx=1&mode=Basic&vid=SUVU01&vl(96071691UI1)=all_items&dscnt=0&vl(54032236UI0)=lsr02&srt=rank&ct=facet&frbg=&fctV=include%20only%20journals%20or%20serials&scp.scps=scope%3A(SU)&indx=1&dum=true&dstmp=1269964178144&fctN=facet_fmt&fn=search&vl(freeText0)=Organometallics&tab=local
    Subjects:Science > Science (General)
    Science > Chemistry
    Science > Chemistry > Physical and theoretical chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Strathprints Administrator
    Date deposited:01 Apr 2010 11:39
    Last modified:11 Nov 2024 09:23
    URI:https://strathprints.strath.ac.uk/id/eprint/17013
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