Preparation, characterization, and magnetic behavior of the ln derivatives (ln = nd, la) of a 2,6-diiminepyridine ligand and corresponding dianion

Inorg Chem. 2004 Sep 6;43(18):5771-9. doi: 10.1021/ic049820t.

Abstract

An unprecedented Nd[2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N=C(CH(3))](2)(C(5)H(3)N)]NdI(2)(THF) (1) complex was prepared by oxidizing metallic Nd with I(2) in THF and in the presence of 2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N=C(CH(3))](2)(C(5)H(3)N). The magnetic behavior at variable T clearly indicated that the complex should be regarded as a trivalent Nd atom antiferromagnetically coupled to a radical anion. By using the doubly deprotonated form of the diimino pyridine ligand [[2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N-C=CH(2)](2)(C(5)H(3)N)](2-) (2) the corresponding trivalent complexes [[2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N-C=CH(2)](2)(C(5)H(3)N)]Ln (THF)](mu-Cl)(2)[Li(THF)(2)].0.5 (hexane) [Ln = Nd (3), La (4)] were obtained and characterized. Reduction of these species afforded electron transfer to the ligand system which gave ligand dimerization via C-C bond formation through one of the two ene-amido functions of each molecule. The resulting dinuclear [[([2,6-(i-Pr)(2)C(6)H(5)]N-C=(CH(2)))(C(5)H(3)N)([2,6-(i-Pr)(2)C(6)H(5)]N=CCH(2))]Ln(THF)(2)(mu-Cl)[Li(THF)(3)])(2).2(THF) [Ln = Nd (5), La (6)] were isolated and characterized.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anions / chemistry*
  • Lanthanum / chemistry*
  • Ligands
  • Magnetics*
  • Models, Chemical
  • Molecular Structure
  • Neodymium / chemistry*
  • Organometallic Compounds* / chemical synthesis
  • Organometallic Compounds* / chemistry
  • Pyridines / chemistry*
  • Spectrum Analysis
  • Temperature

Substances

  • Anions
  • Ligands
  • Organometallic Compounds
  • Pyridines
  • Neodymium
  • Lanthanum