{CpFeII(CO)2SnII(Macrocycle•3-)} Radicals with Intrinsic Charge Transfer from CpFe(CO)2 to Macrocycles (Cp: Cp or Cp*); Effective Magnetic Coupling between Radical Trianionic Macrocycles•3-

Neutral {CpFeII(CO)(2)[Sn-II(Pc-center dot(3-))]} {Cp is cyclopentadienyl (1, 2) or Cp* is pentamethylcyclopentadienyl ( 3 ); Pc: phthalocyanine}, {Cp*Fe-II(CO)(2)[Sn (II)(Nc(center dot)(3-))]} (4, Nc: naphthalocyanine), and {CpFeII(CO)(2) [Sn-II(TPP center dot 3-)]} (5, TPP: tetraphenylporphyrin) complexes in which CpFeII(CO)(2) fragments (Cp: Cp or Cp*) are coordinated to Sn-II(macrocycle(center dot)(3-)) have been obtained. The product complexes were obtained at the reaction of charge transfer from CpFeI (CO)(2) (Cp: Cp or Cp*) to [Sn-II(macrocycle(2-))] to form the diamagnetic Fe-II and paramagnetic radical trianionic macrocycles. As a result, these formally neutral complexes contain S = 1/2 spins delocalized over the macrocycles. This provides alternation of the C-N-imine or C-C-meso bonds in the macrocycles, the appearance of new bands in the near-infrared spectra of the complexes, and blue shift of both Soret and Q-bands. The {CpFeII(CO)(2)Sn-II(macrocycle(center dot)(3-))} units (Cp: Cp or Cp*, macrocycle: Pc or Nc) form closely packed sr-stacking dimers in 1 and 3 or one-dimensional chains in 2 and 4 with effective pi-pi interaction between the macrocycles. Such packing allows strong antiferromagnetic coupling between S = 1/2 spins. Magnetic interaction can be described well by the Heisenberg model for the isolated dimers in 1 and 3 with exchange interaction J/k(B)= -78 and -85 K, respectively. Magnetic behavior of 2 and 4 is described well by the model that includes contributions from an antiferromagnetically coupled S = 1/2 dimer (J(intra)) and a Heisenberg S = 1/2 chain with alternating antiferromagnetic spin exchange between the neighbors (J(inter)). Compound 2 demonstrates large intradimer interaction of = -54 K and essentially weaker interdimer exchange interactions of J/k(B) = -6 K, whereas compound 4 shows strong magnetic coupling of spins within the dimers (J(intra)/k(B) = -170 K) as well as between the dimers (J(inter)/k(B) = -40 K). Compound {CpFeII(CO)(2)[Sn-II(TPP center dot 3-)]} (5) shows no pi-pi interactions between the porphyrin macrocycles, and magnetic coupling is weak in this case (Weiss temperature is -5 K). Preparation of a similar complex with indium(III) chloride phthalocyanine yields {CpFe(CO)(2)[In(Pc2-)]} (6). In this complex, indium(III) atoms are reduced instead of the phthalocyanine macrocycles that explains electron paramagnetic resonance silence of 6 in the 4-295 K range.