ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Phthalocyanines of transition metals, with unusually low oxidation states of the central atom

R. Taube

Ernst-Moritz-Arndt Univ., Greifswald, Germany.

Abstract:  The central atom and the total charge of the phthalocyanines (Pc) can be varied without structural change; the properties of the Pc can thus be studied in relation to the at. no. of the central atom, its oxidn. state, and the total no. of electrons of the complex. Ni, Co, Fe, and MnPc were reduced in tetrahydrofuran (THF) with Li and Na and their addn. compds. with C₁₀H₈ and BzPh. The no. of the redn. steps obtained depended on the nature of the central atom and the reducing power of the reducing compd. in the order Li, Na > Li₂C₁₀H₈, NaC₁₀H₈ > Li₂BzPh > LiBzPh. The degrees of redn. obtained were: NiPc 1-4, CoPc 1-5, FePc 1-4, MnPc 1-4. All compds. are air-sensitive, the Ni, Co, and Fe compds. being oxidized to the starting Pc. The corresponding Li and Na compds. have similar colors, but differ in their soly. Characterized in detail are Li[NiPc].4.5 THF (I), Li₂[NiPc].6 THF (II), Li[CoPc].4.5 THF (III), Li₂[CoPc].6 THF (IV), Li[FePc].4.5 THF (V), Li₂[FePc].5.5 THF (VI), Li[MnPc].6 THF (VII), Li₂[MnPc].6 THF (VIII), Li₃[MnPc].9 THF (IX). I, III, V, and VII were prepared by redn. with 0.5Li₂BzPh, II and VI with 1Li₂BzPh, IV and VIII with 2Li₂BzPh, and IX with 3 LiBzPh. These compds. are sol. with intense colors in polar solvents such as THF, MeCN, HCONMe₂, and pyridine. The no. of unpaired electrons which was derived from magnetic measurements is in full accordance with the stepwise change of the total no. of electrons. Semiempirical mol. orbital calcns. according to Hueckel are in accord with the detd. magnetic moments, except for II.

Full paper in Portable Document Format: 193a215.pdf (in German)

Chemical Papers 19 (3) 215–220 (1965)