Addition of carbenes to an osmium(VI) nitride complex

Chi Fai LEUNG, Tsz-Wing WONG, Tai-Chu LAU, Wing-Tak WONG

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19 Citations (Scopus)

Abstract

A series of osmium(VI) nitride complexes containing 8-quinolinolato ligands, [Osⱽᴵ(N)(X-Q)₂Cl] (X = H, 5-Cl, 5-NO₂, 2-Me; 1a-d), have been synthesized by reaction of HX-Q with [nBu₄N][Osⱽᴵ(N)Cl₄] in the presence of 2,6-dimethylpyridine. The v(Os≡N) stretches of these compounds occur at 1056-1075 cm⁻¹, and are within the range (1050-1120 cm⁻¹) found for most osmium nitride species. The structure of 1d has been determined by X-ray crystallography. The osmium center adopts a distorted octahedral geometry, and the two quinolinolato ligands are cis to each other. The three N atoms are in a facial arrangement, and the Os≡N bond distance is 1.644(6) Å. Complex 1c readily reacts with the carbene precursors bis(1,3-dialkylimidazolidin-2-ylidene) (Lᴿ₂; R = Me, Et, or CH₂Ph) to produce the osmium(IV) azavinylidene species, [Osᴵⱽ(N=Lᴿ)(NO₂-Q)₂Cl], which are derived from the formal addition of the carbenes Lᴿ to Osⱽᴵ≡N. The structure of [Osᴵⱽ(N=Lᴱᵗ) (NO₂₋Q)₂Cl] (2b) has been determined by X-ray crystallography. The osmium center has a distorted octahedral geometry in which the facial arrangement of the three N atoms is retained. The Os(1)-N(5) distance of 1.875(6) Å is rather long and, together with the rather acute Os(1)-N(5)-C(19) angle of 133.8(5)°, indicates that there is no significant multiple-bond character in the Os(1)-N(5) bond. Copyright © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Original languageEnglish
Pages (from-to)773-778
JournalEuropean Journal of Inorganic Chemistry
Volume2005
Issue number4
DOIs
Publication statusPublished - Feb 2005

Citation

Leung, C.‐F., Wong, T.‐W., Lau, T.‐C., & Wong, W.‐T. (2005). Addition of carbenes to an osmium(VI) nitride complex. European Journal of Inorganic Chemistry, 2005(4), 773-778. doi: 10.1002/ejic.200400539

Keywords

  • Carbenes
  • N,O ligands
  • Nitrides
  • Osmium
  • Vinylidene ligands

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