Investigations of the Technetium-Hydrazido Core. Synthesis and Structural Characterization of [(n-C4H9)4N][Tc2(NNPh2)2(C6Cl4O2)4]•CH2Cl2•2CH3OH, a Tc(V)/Tc(VI) Catecholate Complex with the Hydrazido Ligands Adopting the Unusual η1 Bridging Mode

Michael J. Abrams, Scott K. Larsen, Jon Zubieta

Research output: Contribution to journalArticle

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Abstract

Reaction of the oxo-bis(tetrachlorocatecholate) Tc(V) complex [(n-C4H9)4N] [TcO(C6Cl4O2)2] (1) with N,N-diphenylhydrazine in CH2Cl2 yields the binuclear paramagnetic Tc(V)/Tc(VI) mixed-valence complex [(n-C4H9)4N][Tc2(NNPh2)2(C6Cl4O2)4]•CH2Cl2•2CH3OH (2). The structure of the molecular anion of 2 consists of two distorted octahedral Tc centers bridged by two hydrazido(2-) groups bonding in the η1 mode, an unusual bonding motif for this ligand, having been previously described only for cyclopentadienyl-metal species. Complex 2 is also a unique example of a Tc(V)/Tc(VI) mixed-valence species; the Tc-Tc distance of 2.612 (2) Å is consistent with direct metal-metal interaction. Crystal data for 1: P1, a = 9.579 (2) Å, b = 11.705 (3) Å, c = 16.391 (4) Å, α = 83.95 (2)°, β = 88.63 (2)°, 7 = 74.51 (2)°, V= 1761.3 (7) Å3, Z = 2, Dcalc = 1.60 g cm-3; 3637 reflections, R = 0.046. Crystal data for 2: P1, a = 14.210 (3) Å, * = 16.663 (4) Å, c = 19.644 (4) Å, a = 76.82 (2)°, β = 80.52 (2)°, γ = 66.79 (2)°, V = 4151.8 (15) Å3, Z = 2, Dcalc = 1.55 g cm-3; 6999 reflections, R = 0.075.

Original languageEnglish (US)
Pages (from-to)2031-2035
Number of pages5
JournalInorganic Chemistry
Volume30
Issue number9
DOIs
StatePublished - May 1 1991

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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