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

D.R. Armstrong, C. Dougan, D.V. Graham, E. Hevia, A.R. Kennedy

Research output: Contribution to journalArticle

26 Citations (Scopus)

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.
LanguageEnglish
Pages6063-6070
Number of pages7
JournalOrganometallics
Volume27
Issue number23
DOIs
Publication statusPublished - 8 Dec 2008

Fingerprint

anisole
ligands
synthesis
zinc
Ligands
solid state
Discrete Fourier transforms
Zinc
x rays
X rays
phenyllithium
Substrates
benzonitrile

Keywords

  • synthesis
  • structural elucidation
  • alkyl
  • amido
  • mixed alkyl−amido
  • "highly-coordinated” zincates

Cite this

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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 Br{\o}nsted base for metalation (zincation) of functionalized aromatic substrates such as anisole, N,N-diisopropylbenzamide, and benzonitrile.",
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Synthesis and structural elucidation of alkyl, amido, and mixed. alkyl-amido "highly-coordinated" zincates. / Armstrong, D.R.; Dougan, C.; Graham, D.V.; Hevia, E.; Kennedy, A.R.

In: Organometallics, Vol. 27, No. 23, 08.12.2008, p. 6063-6070.

Research output: Contribution to journalArticle

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T1 - Synthesis and structural elucidation of alkyl, amido, and mixed. alkyl-amido "highly-coordinated" zincates

AU - Armstrong, D.R.

AU - Dougan, C.

AU - Graham, D.V.

AU - Hevia, E.

AU - Kennedy, A.R.

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N2 - 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.

AB - 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.

KW - synthesis

KW - structural elucidation

KW - alkyl

KW - amido

KW - mixed alkyl−amido

KW - "highly-coordinated” zincates

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