The synthesis and characterization of a cationic technetium(V) phenylimido complex. The X-ray crystal structure of [TcCl2(NPh)(PMe2Ph)3](BPh4)

Terrence Nicholson, Alan Davison, Jon A. Zubieta, Qin Chen, Alun G. Jones

Research output: Contribution to journalArticle

16 Scopus citations

Abstract

The reaction of the neutral Tc(V) phenylimido complex [TcCl3(NPh)(PPh3)2] with excess PMe2Ph in refluxing MeOH gives the cationic, tris-dimethylphenylphosphine complex [TcCl2(NPh)(PMe2Ph)3]+, which is isolated as the tetraphenylborate salt. The IR spectrum of the crystalline product shows a medium intensity band at 1102 cm-1 which is assigned to ν(TcN) from the phenylimido core. The 1H NMR spectrum of the diamagnetic complex shows a series of multiplets in the aryl region and three distinct signals near 2 ppm from the phosphine methyl groups. The X-ray crystal structure, which is the first for a cationic technetium organoimido complex, shows a meridional arrangement of phosphine ligands with a chloride ligand coordinated trans to the phenylimido unit. The TcN bond length of 1.711(2) Å is consistent with the dianionic nature of the organonitrogen core. The TcNC bond angle of 178.8(2)° reflects the sp hybridization of the phenylimido nitrogen atom. The coordination geometry is best described as a distorted octahedron. Crystal data for C54H58BCl2NP3Tc: triclinic space group P1, a = 11.337(2), b = 13.054(3), c = 17.854(4) A ̊, α = 72.36(3), β = 88.51(3), γ = 89.76(3)°, V = 2517.2(13) A ̊3, with Dcalc = 1.311 g cm-3. Structure solution based on 9986 observed reflections converged at R = 3.65%, Rw = 5.43%, GOF = 1.82.

Original languageEnglish (US)
Pages (from-to)205-208
Number of pages4
JournalInorganica Chimica Acta
Volume230
Issue number1-2
DOIs
StatePublished - Mar 1 1995

Keywords

  • Crystal structures
  • Imido complexes
  • Technetium complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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