A series of complexes of the phosphorus-based TTF ligand o -P2 with the metal ions Fe II , Co II , Ni II , Pd II , Pt II , and Ag I Academic Article uri icon

abstract

  • Reactions of 3,4-dimethyl-3',4'-bis(diphenylphosphino)tetrathiafulvalene, o-P2, with [BF(4)](-) salts of Fe(ii), Co(ii), Ni(II), Pd(II), and Pt(II) yield complexes of general formula [M(o-P2)(2)][BF(4)](2). Similar reactions between o-P2 and AgSbF(6) or AgPF(6) produced the salts [Ag(o-P2)(2)][X] where X = [SbF(6)](-) or [PF(6)](-). The resulting compounds were fully characterized by (1)H and (31)P{(1)H} NMR, infrared and electronic absorption spectroscopies, cyclic voltammetry, FAB-MS and single-crystal X-ray diffraction. The paramagnetic Co(II) compound exhibits an S = 3/2 state with large spin-orbit coupling contribution at higher temperatures and an effective S' = 1/2 state below 20 K. Electrochemical studies of the compounds indicate that the two functionalized TTF ligands are not in electronic communication and that they essentially behave as isolated redox centers.

author list (cited authors)

  • Uzelmeier, C. E., Smucker, B. W., Reinheimer, E. W., Shatruk, M., O'Neal, A. W., Fourmigu√©, M., & Dunbar, K. R.

citation count

  • 33

publication date

  • January 2006