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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

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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.

Item type: Article
ID code: 17013
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
Keywords: synthesis, structural elucidation, alkyl, amido, mixed alkyl−amido, "highly-coordinated” zincates, Science (General), Chemistry, Physical and theoretical chemistry, Organic Chemistry, Physical and Theoretical Chemistry, Inorganic Chemistry
Subjects: Science > Science (General)
Science > Chemistry
Science > Chemistry > Physical and theoretical chemistry
Department: Faculty of Science > Pure and Applied Chemistry
Related URLs:
    Depositing user: Strathprints Administrator
    Date Deposited: 01 Apr 2010 12:39
    Last modified: 05 Sep 2014 02:51
    URI: http://strathprints.strath.ac.uk/id/eprint/17013

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