Coordination of tin(II) phthalocyanine to transition metal carbonyl clusters in neutral {Sn(II){Pc(2-)}}(0) or radical anion {Sn(II){Pc(•3-)}}(-) states is reported. Direct interaction of Co4(CO)12 with {Sn(II){Pc(2-)}}(0) yields crystalline complex {Co4(CO)11·Sn(II){Pc(2-))} (1)....

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Coordination complex (Cp*2CrIII)+{CpFeII(CO)2(SnII[PcCl16]4−)}−(1) has been obtained by the reduction of tin(IV) dichloride hexadecachlorophthalocyanine (PcCl16) by decamethylchromocene (Cp*2Cr) in the presence of {CpFeI(CO)2}2. The process is accompanied by oxidation of CrII...

Reduction of iron(II) octaethyltetrapyrazinoporphyrazine, FeIITPyzPzEt8, by zinc dust allowed the preparation of crystalline salt (PPN+)2{FeII(TPyzPzEt8)4–(ZnCl2)2}2– (1) (PPN+ is bis(triphenylphosphoranylidene)ammonium). Metal atom zinc transfers two electrons to FeIITPyzPzEt8 forming the {Fe(TPyzPzEt8)}2– dianions which coordinate two ZnCl2 units on the periphery of the TPyzPzEt8 macrocycle. Tetrahedral environment around the zinc(II) atoms is formed with the length of the Zn–N bonds of 2.071(7) Å with meso‐ and 2.304(8) Å with pyrazine nitrogen atoms of TPyzPzEt8. Optical and EPR spectra show the formation of diamagnetic tetraanionic {TPyzPzEt8}4– macrocycle in 1, and as a result, two‐electron reduction of FeIITPyzPzEt8 is centered exclusively on the macrocycle. According to DFT calculations for the {Fe(TPyzPzMe8)(ZnCl2)2}2– and {Fe(TPyzPzMe8)}2– dianions the reason of that is strongly increased electron affinity of the TPyzPzMe8 macrocycle at the coordination of two ZnCl2 units. Obviously, this situation is different from iron(II) phthalocyanine which shows metal‐centered first and second reduction.