Coordination complexes of iron(II) phthalocyanine with cationic, anionic and neutral ligands

A series of coordination complexes of iron(II) phthalocyanine (Fe II Pc) with anionic, cationic and neutral ligands has been obtained in crystalline form. The salt of Fe II Pc with MDABCO[Formula: see text] cations (MDABCO[Formula: see text][Fe I (Pc[Formula: see text]][Formula: see text]⋅(I[Formula: see text]⋅2TPC⋅2C 6 H 4 Cl 2 (1) contains Fe II Pc reduced to [Fe I (Pc[Formula: see text]][Formula: see text], and the Fe I ion coordinates two cationic MDABCO[Formula: see text] ligands with the Fe-N(MDABCO[Formula: see text] bond length of 2.49–2.50 Å. The I[Formula: see text] anions are introduced into the phthalocyanine layers to compensate positive charge of the second MDABCO[Formula: see text] cation and form short hydrogen bonds with Pc. Preparation of dianionic salt of Fe II Pc with the Bu 3 MeP[Formula: see text] cations by their reduction with sodium fluorenone ketyl yields a green solution characteristic of neutral Fe II Pc. The solved structure shows deprotonation of the cations and the formation of Bu 3 PCH 2 ylide which coordinates to Fe II Pc in (Bu 3 PCH[Formula: see text][Fe II (Pc[Formula: see text]] (2). Two anionic acetylide (C[Formula: see text]CH[Formula: see text] or imidazole (Im[Formula: see text] ligands coordinate to Fe II Pc by dissolving with cryptand and yielding {Cryptand(Na[Formula: see text]} 2 {(CCH[Formula: see text]Fe II (Pc[Formula: see text]}⋅2C 6 H 4 Cl 2 (3) and {Cryptand(Na[Formula: see text]} 2 {(Im[Formula: see text]Fe II (Pc[Formula: see text]}⋅2C 6 H 4 Cl 2 (4) complexes. In contrast to 1, complexes 2–4 are mainly neutral with weak charge transfer from ligands to Fe II , which is accompanied by the formation of Fe I in 2 and 3.