Synthesis, structure, and magnetic and electrochemical properties of quasi-linear and linear iron(I), cobalt(I), and nickel(I) amido complexes

Chun Yi Lin, James C. Fettinger, Fernande Grandjean, Gary J. Long, Philip P. Power

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

Three potassium crown ether salts, [K(Et2O)2(18- crown-6)][Fe{N(SiMe3)Dipp}2] (1a; Dipp = C 6H3-2,6-Pri2), [K(18-crown-6)] [Fe{N(SiMe3)Dipp}2]·0.5PhMe (1b), and [K(18-crown-6)][M{N(SiMe3)Dipp}2] (M = Co, 2; M = Ni, 3), of the two-coordinate linear or near-linear bis-amido monoanions [M{N(SiMe 3)Dipp}2]- (M = Fe, Co, Ni) were synthesized by one-electron reduction of the neutral precursors M{N(SiMe3)Dipp} 2 with KC8 in the presence of 18-crown-6. They were characterized by X-ray crystallography, UV-vis spectroscopy, cyclic voltammetry, and magnetic measurements. The anions feature lengthened M-N bonds in comparison with their neutral precursors, with slightly bent coordination (N-Fe-N = ca. 172°) for the iron(I) complex, but linear coordination for the cobalt(I) and nickel(I) complexes. Fits of the temperature dependence of χMT of 1 and 2 reveal that the iron(I) and cobalt(I) complexes have large negative D zero-field splittings and a substantial orbital contribution to their magnetic moments with L = 2, whereas the nickel(I) complex has at most a small orbital contribution to its magnetic moment. The magnetic results have been used to propose an ordering of the 3d orbitals in each of the complexes.

Original languageEnglish
Pages (from-to)9400-9406
Number of pages7
JournalInorganic Chemistry
Volume53
Issue number17
DOIs
Publication statusPublished - 2014 Sep 2

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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