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Treatment of [HN[[Bu.sub.3].sub.3]][Mo.sup.V](CN)[.sub.8] with manganese(II) p-toulenesulfonate in DMF affords {[Mn.sup.II](DMF).sub.4].sub.3][[Mo.sup.V][(CN).sub.8].sub.2].sub.n} as a two-dimensional network. Magnetic measurements indicate that {[Mn.sup.II](DMF)[sub.4]][sub.3][[Mo.sup.V][(CN).sub.8].sub.2].sub.n} is a ferrimagnet that exhibits frequency-dependent behavior in chi'.

Abstract: Treatment of several binary transition metal p-toluenesulfonates [MII(OTs)2] with tri(butyl)ammonium octacyanomolybdate(V) or -tungstate(V) in DMF readily affords a series of one- and two-dimensional crystalline octacyanometalate networks of [MII(DMF)4]3[MV(CN)8]2 (MV =Mo, W; MII =Mn, 5, 6; Ni, 7, 8) stoichiometry. Treatment of Fe(OTs)2 with [HBu3N]3[WV(CN)8] in DMF affords amorphous precipitates while FeCl3 affords crystalline [FeII(DMF)6]2[WIV(CN)8] (9) salts; two-dimensional [FeII(DMF)4]3[WV(CN)8]2 (10) lattices are obtained from 9 after standing several months. The structures of 5 and 8 contain [cis-MII(DMF)4(μ-NC)2]2+ and [trans-MII(DMF)4(μ-NC)2]2+ units that are linked via cyanides to three-connected [MV(CN)5(μ-CN)3]3− centers, forming a one-dimensional chain of squares that crystallize in the monoclinic (5, P21/n) and triclinic (8,) space groups; 6 (P21/n) and 10 (P21/c) crystallize as two-dimensional corrugated sheets containing [cis-MII(DMF)4(μ-NC)2]2+, [trans-MII(DMF)4(μ-NC)2]2+, and [MV(CN)5(μ-CN)3]3− units in a 4:2:6 ratio. Magnetic measurements indicate that 6 is a ferrimagnet (T N =8K) that exhibits frequency-dependent behavior in χ″ that is qualitatively similar to 1- and 2-D lattices reported by Tang and Holmes, respectively; dc magnetic measurements suggest that 5, 7, and 8 exhibit incipient magnetic ordering while ac measurements show no frequency-dependent behavior in χ″. Surprisingly, conversion of 5 to 6 in the presence of counterions occurs while heating crystalline samples introduces additional magnetic phases without linkage isomerism; two-dimensional phases containing MnII centers appear to be the sole product when wet DMF is used as a reaction solvent. The experimental evidence suggests that coordinated DMF ligands are labile and the MII(μ-NC)MV linkages are susceptible to fragmentation. [Copyright &y& Elsevier]

Treatment of [HNBu3]3[MoV(CN)8] with manganese(II) p-toluene-sulfonate in N,N′-dimethylformamide (DMF) affords {[MnII(DMF)4]3-[MoV(CN)8]2}n (1) as a two-dimensional network. The structure of 1 consists of [cis-MnII(DMF)4(μ-NC)2]2+ and [trans-MnII(DMF)4(μ-NC)2]2+ units that are linked via cyanides to three-connected [MoV-(CN)5(μ-CN)3]3- centers in a 4:2:6 ratio, forming 12-membered rings. Magnetic measurements indicate that 1 is a ferrimagnet (TN = 8 K) that exhibits frequency-dependent behavior in χ″. Heating of 1 affords an additional magnetic phase (TN = 21 K) that is absent of linkage isomerism. [ABSTRACT FROM AUTHOR]

The syntheses and structures of three dicyanometalate(II) complexes, [NEt(4)][(Tp*)M(II)(CN)(2)].nMeCN.(1/2)Et(2)O (M(II) = Cr, 1, n = (1/2); Co, 2, n = 1; Ni, 3, n = 1) are described; magnetic studies indicate that 3 is diamagnetic while 1 and 2 are paramagnetic high- and low-spin S = 2 and (1/2) complexes, respectively.