Structure dependence on redox state and charge in [Fe_4(#mu#_3-S_4)-(#eta#-C_5H_5)_4]_m[M(mnt)_2]n (M = Ni or Pt, m, n = 1 or 2)

摘要

The complex salts (Fe_4(#mu#_3-S)_4(#eta#-C_5H_5)_4]_m {M = Ni, n = 2, m = 1 1; n = 1, m = 1 2 or 2 3: M = Pt, n = 2, m = 1 4; n = 1, m = 1 5 or 2 6; mnt = S_2C_2(CN)_2} have been synthesized by stoichiometric reactions between [Net_4]_n-[M(mnt)_2] (n = 1 or 2, M = Ni or Pt) and [Fe_4(#mu#_3-S)_4(#eta#-C_5H_5)_4][PF_6]_n (n = 1 or 2); the salts 2-6 have been structuraly characterised. The molecular structures of the [Fe_4(#mu#_3-S)_4(#eta#-C_5H_5)_4]~(z+) (z = 1 or 2) cations and the [M(mnt)_2]~(z-) (M = Ni or Pt, z = 1 or 2 anions show mean Fe…Fe and M-S distances characteristic of z. The isostructural satls [Fe_4(#mu#_3-S)_4(#eta#-C_5H_5)_4]_2[M(mnt)_2] (M = Ni 3 or Pt 6) comprise two monocations and one dianion; the planar anions, which form a ruffled ribbon arrangement, are interleaved by the near-spherical cations. The structure of [Fe_4(#mu#_3-S)_4(#eta#-C_5H_5)_4][Pt(mnt)_2]_2, 4, with two monoanions and one dication, has face-to-face metal-metal pairs of [Pt(mnt)_2]~- ions separated by individual [Pt(mnt)_2]~- units, leading to anion layers interleaved by layers of cations. Salts 2 and 5 have very different strucutres. The nickel complex [Fe_4(#mu#_3-S)_4][Ni(mnt)_2] 2 comprises dications and dianions whereas the platinum complex [Fe_4(#mu#_3-S)_4(#eta#-C_5H_5)_4][Pt(mnt)_2] 5 has monocations and monoanions. In salt 2 the dianions are well separated while in 5 the monoanions are weakly dimerised.