Coordination chemistry of higher oxidation states. 25. Synthesis and properties (including 59Co NMR spectra) of cobalt(III) complexes of ligands containing two tertiary stibine groups. Crystal structure of trans -[Co{o-C6H4(SbMe2)2}2Cl2]2[CoCl4]

Hilary C. Jewiss, William Levason*, Mark D. Spicer, Michael Webster

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

27 Citations (Scopus)

Abstract

Cobalt(III) complexes of two ligands containing two tertiary stibine groups, [Co{oC6H4(SbMe2)2)2X2]X (X = Cl, Br, I) and [Co{Me2Sb(CH2)3SbMe2)2X2]X (X = Br, I), have been prepared and shown to have trans pseudooctahedral cations. The synthesis of trans-[Co(o-C6H4(SbMe2)(PMe2)}2X2]Y (X = Cl, Br, I; Y =X, BF4), trans-[Co{o-C6H4(PPh2)(SMe))2X2]BF4, trans-[Co{o-C6H4(PPh2)(SeMe)}2X2]BF4(X = Cl, Br), and fac-[Co{o-C6H4(PPh2)(SMe)}3](BF4)3 are described. The complexes have been characterized by UV-visible spectroscopy and multinuclear (1H,31P{1H), 77Se{1H}) NMR as appropriate. 59Co NMR spectra are reported for these complexes, and the characteristic ranges of the 59Co chemical shifts for Co(III) complexes containing neutral heavy groups VB and VIB (groups 15 and 16) donor ligands are established. The X-ray structure of [Co{o-C6H4-(SbMe2)2)2Cl2]2[CoCl4] has been determined. Crystals belong to the tetragonal system, space group 141/a (No. 88), with a = 25.264 (6) Å, c = 9.720 (9) Å, and Z = 4. The structure was refined to an R of 0.058 from 1237 observed reflections (F> 3σ(F)). The cobalt of the cation is located on a center of symmetry (Co-Sb = 2.505 (1), 2.478 (1) Å; Co-Cl = 2.263 (4) Å), and the anion has 4 symmetry (Co-Cl = 2.287 (6) Å).

Original languageEnglish
Pages (from-to)2102-2106
Number of pages5
JournalInorganic Chemistry
Volume26
Issue number13
DOIs
Publication statusPublished - 1 Jul 1987
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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