Nitrido-ruthenium(vi) and -osmium(vi) complexes of multianionic chelating (N, O) ligands. Reactions with nucleophiles, electrophiles and oxidizing agents

Ka Lai Yip, Wing Yiu Yu, Pui Ming Chan, Nian Yong Zhu, Chi Ming Che

Research output: Journal article publicationJournal articleAcademic researchpeer-review

23 Citations (Scopus)

Abstract

This account presents the diverse reactivity of nitridoruthenium(vi) complexes with nucleophilic, electrophilic and oxidizing agents. [RuVI(N)(L1)Cl] (1)[H2L1= 2,6-bis(2,2-diphenyl-2-hydroxyethyl)pyridine] reacted with excess phosphines such as PPh3, PPhMe2and dppe to give [RuIII(HL1)(PPh3)Cl2](2a), [RuIII(L1)(PPhMe2)2Cl](2b) and [RuIII(L1)(dppe)Cl](2c), respectively. In the presence of py or Hpz, 1 was converted to [RuIII(L1)(py)2Cl](3a) and [RuIII(L1)(Hpz)3]Cl (3b), respectively. A dinuclear μ-nitridoruthenium complex, [RuIV(L1)Cl2(μ-N)RuVI(L1)(C8H10N)Cl](4), was obtained by treating 1 with 2,6-dimethylaniline. Based on X-ray crystallographic study, the compound is characterized by an unsymmetrical Ru–N≡Ru moiety with the measured Ru–N distances being 1.661(5) and 1.837(5)Å. Complex 1 reacted with dmf to give [RuIII(HL1)(dmf)Cl2](5) in 17% yield. Excess (Me3O)BF4reacted with 1 to give a dinuclear μ-OH ruthenium complex, [Ru2(N)2(L1)2(OH)]PF6(6). The measured Ru–O(OH)distance is 1.984(3)Å and the average Ru–O–Ru angle was found to be 100.4(2)°. Other nitrido-metal complexes, [n-Bu4N][MVI(N)(L)][L = L2and L3; M = Os and Ru; H4L2= 1,2-dichloro-4,5-bis(2-hydroxybenzamido)benzene, H4L3= 1,2-bis(2-hydroxybenzamido)benzene], underwent ligand protonation to form [MVI(N)(HL)] complexes, which have been characterized by X-ray crystallography. Oxidation of [n-Bu4N][OsVI(N)(L2)] by PhI(OAc)2produced [n-Bu4N][OsVI(N)(L2O2)](8) in 10% yield. X-ray structure analysis of 8 showed that the coordinated phenoxy moiety was converted to a benzoquinone moiety while the Os≡N group remained intact.
Original languageEnglish
Pages (from-to)3556-3566
Number of pages11
JournalJournal of the Chemical Society. Dalton Transactions
Volume3
Issue number18
DOIs
Publication statusPublished - 5 Aug 2003
Externally publishedYes

Keywords

  • Coordination chemistry
  • Macrocycles
  • Osmium
  • P, N, S, Se, O, Te, Si-containing ligands
  • Ruthenium

ASJC Scopus subject areas

  • Chemistry(all)

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