Coordination Complexes of Transition Metals (M = Mo, Fe, Rh, and Ru) with Tin(II) Phthalocyanine in Neutral, Monoanionic, and Dianionic States

The ability of tin atoms to form stable Sn–M bonds with transition metals was used to prepare transition metal complexes with tin­(II) phthalocyanine in neutral, monoanionic, and dianionic states. These complexes were obtained via the interactions of [SnIVCl2Pc­(3−)]•– or [SnIIPc­(3−)]•– radical anions with {Cp*Mo­(CO)2}2, {CpFe­(CO)2}2, {CpMo­(CO)3}2, Fe3(CO)12, {Cp*RhCl2}2, or Ph5CpRu­(CO)2Cl. The neutral coordination complexes of Cp*MoBr­(CO)2[SnIIPc­(2−)]·0.5C6H4Cl2 (1) and CpFe­(CO)2[SnIIPc­(2−)]·2C6H4Cl2 (2) were obtained from [SnIVCl2Pc­(3−)]•–. On the other hand, the coordination of transition metals to [SnIIPc­(3−)]•– yielded anionic coordination complexes preserving the spin on [SnIIPc­(3−)]•–. However, in the case of {cryptand­[2,2,2]­(Na+)}­{CpFeII(CO)2[SnIIPc­(4−)]}−·C6H4Cl2 (4), charge transfer from CpFeI(CO)2 to [SnIIPc­(3−)]•– took place to form the diamagnetic [SnIIPc­(4−)]2– dianion and {CpFeII(CO)2}+. The complexes {cryptand­[2,2,2]­(Na+)}­{Fe­(CO)4[SnIIPc­(3−)]•–} (5), {cryptand­[2,2,2]­(Na+)}­{CpMo­(CO)2[SnIIPc­(2−)­SnIIPc­(3−)•–]} (6), and {cryptand­[2,2,2]­(Na+)}­{Cp*RhCl2[SnIIPc­(3−)]•–} (7) have magnetic moments of 1.75, 2.41, and 1.75 μB, respectively, owing to the presence of S = 1/2 spins on [SnIIPc­(3−)]•– and CpMoI(CO)2 (for 6). In addition, the strong antiferromagnetic coupling of spins with Weiss temperatures of −35.5 −28.6 K was realized between the CpMoI(CO)2 and the [SnIIPc­(3−)]•– units in 6 and the π-stacking {Fe­(CO)4[SnIIPc­(3−)]•–}2 dimers of 5, respectively. The [SnIIPc­(3−)]•– radical anions substituted the chloride anions in Ph5CpRu­(CO)2Cl to form the formally neutral compound {Ph5CpRuII(CO)2[SnIIPc­(3−)]} (8) in which the negative charge and spin are preserved on [SnIIPc­(3−)]•–. The strong antiferromagnetic coupling of spins with a magnetic exchange interaction J/kB = −183 K in 8 is explained by the close packing of [SnIIPc­(3−)]•– in the π-stacked {Ph5CpRuII(CO)2[SnIIPc­(3−)]•–}2 dimers.