Inorganic Chemistry, Vol.44, No.2, 352-358, 2005
Synthesis and structural characterization of bi- and trimetallic Octacyanometalate(IV) complexes: [Delta,Lambda-M-II(en)(3)][cis-M-II(en)(2)(OH2)][M-IV(CN)(8)]center dot 2H(2)O and [cis-M-II(en)(2)(OH2)](2)[(mu-NC)(2)M-IV(CN)(6)]center dot 4H(2)O (M-II = Mn, Co, Ni; M-IV = Mo, W)
Treatment of [M-II(en)(3)][OTs](2) or methanolic ethylenediamine solutions containing transition metal p-toluenesulfonates (M-II = Mn, Co) with aqueous K4MIV(CN)(8).2H(2)O or Cs3MV(CN)(8) (M-IV = Mo, W; M-V = Mo) affords crystalline clusters of [M-II(en)(3)][cis-M-II(en)(2)(OH2)(mu-NC)M-IV(CN)(7)].2H(2)O (M-IV = Mo; M-II = Mn, 1; Ni, 5; M-IV = W; M-II = Mn, 2; Ni, 6) and [cis-M-II(en)(2)(OH2)](2)[(mu-NC)(2)M-IV(CN)(6)].4H(2)O (M-IV = Mo; M-II = Co, 3; Ni, 7; M-IV = W; M-II = Co, 4) stoichiometry. Each cluster contains cis-M-II(en)(2)(OH2)(mu-NC)(2+) units that likely result from dissociative loss of en from [M-II(en)(3)](2+), affording cis-M-II(en)(2)(OH2)(2)(2+) intermediates that are trapped by M-IV(CN)(8)(4-).