Syntheses and structures of highly hindered N-functionalised alkyl and amido group 12 complexes MR2 (M=Zn, Cd, and Hg), [MRCl]2 (M=Zn and Hg)

Tania R. van den Ancker, Lutz M. Engelhardt, Mark J. Henderson, Geraldine E. Jacobsen, Colin L. Raston, Brian W. Skelton, Allan H. White

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)

Abstract

The reaction of MCl2 (M=Zn, Cd and Hg) with Li(2-(C(SiMe3)2)(6-Me-C5 H3N)), [Li(MeR)], affords mononuclear metal(II) alkyls. These, in the solid state, show intramolecular M-N interactions in their four-membered chelate rings, which progressively weaken down the series, the C-M-C angles becoming more open (〈M-N〉= 2.30(2), 2.52(2), 2.913(4) Å, C-M-C=160.7(2), 168.5(2), 180(-)°). Alkylmercury chloride complexes have been prepared by the reaction of HgCl2 with [Li(MeR)], Li(2-(C(SiMe3)2) (C5H4N)), [Li(HR)], or Li(2-(NSiMe3) (6-Me-C5H3N)), [Li(mpsa)], or from the redistribution reaction of the dialkyl (or amido) mercury complex with HgCl2. The alkylmercury chloride complexes are dimeric or polymeric in nature with near-linear 2-coordination; (Hg-Cl=2.329(5), 2.318(4), 2.272(8) Å, Cl-Hg-C(N)=175.0(4), 174.7(4), 175.6(5)°). Cd(2-(CH(SiMe3)) (6-Me-C5H3N))2(tmen), prepared from the reaction of Li(2-(CH(SiMe3)) (6-Me-C5H3N)) and CdCl2 in the presence of tmen, has also been structurally authenticated as the rac isomer with the ipso protons directed towards the tmen.

Original languageEnglish
Pages (from-to)1991-1999
Number of pages9
JournalJOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume689
Issue number11
DOIs
Publication statusPublished - 1 Jun 2004
Externally publishedYes

Keywords

  • Group 12
  • Intramolecular
  • N-functionalised alkyl and amido

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