Redox-active behavior of the [{Ti(η(5)-C5Me5)(μ-NH)}3(μ3-N)] metalloligand

Inorg Chem. 2013 May 20;52(10):6103-9. doi: 10.1021/ic400463a. Epub 2013 May 1.

Abstract

Treatment of [Cl3Y{(μ3-NH)3Ti3(η(5)-C5Me5)3(μ3-N)}] with [K(C5Me5)] in toluene gives C10Me10 and the paramagnetic [K(μ-Cl)3Y{(μ3-NH)3Ti3(η(5)-C5Me5)3(μ3-N)}] (3) derivative. Crystallization of 3 in pyridine affords the potassium-free [Cl2(py)2Y{(μ3-NH)3Ti3(η(5)-C5Me5)3(μ3-N)}] (4) complex. Whereas the reaction of 3 with 1 equiv of 18-crown-6 leads to the molecular complex [(18-crown-6)K(μ-Cl)3Y{(μ3-NH)3Ti3(η(5)-C5Me5)3(μ3-N)}] (5), the analogous treatment of 3 with cryptand-222 affords the ion pair [K(crypt-222)][Cl3Y{(μ3-NH)3Ti3(η(5)-C5Me5)3(μ3-N)}] (6). The X-ray crystal structures of 4, 5, and 6 have been determined. Density functional theory (DFT) calculations have elucidated the electronic structure of these species, which should be regarded as containing trivalent Y bonded to the {(μ3-NH)3Ti3(η(5)-C5Me5)3(μ3-N)} metalloligand radical anion.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Crystallography, X-Ray
  • Ligands
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis
  • Organometallic Compounds / chemistry*
  • Oxidation-Reduction
  • Titanium / chemistry*

Substances

  • Ligands
  • Organometallic Compounds
  • Titanium