Triphenylphosphinoxid (L) als Solvens und Ligand für Metallphthalocyaninate; Synthese und Struktur von [{Li(L)}2(μ‐pc)], [Li(L)4][Lipc] · Solvat, [Mg(L)pc] · Solvat und [Zn(L)pc] · Solvat

Triphenylphosphine Oxide (L) as Solvent and Ligand for Metallophthalocyaninates; Synthesis and Structure of {Li(L)}₂(μ‐pc)], Li(L)₄]Lipc] · Solvate, Mg(L)pc] · Solvate, and Zn(L)pc] · Solvate Triphenylphosphine oxide (L) coordinates to metallophthalocyaninates of Li, Mg and Zn at 300 °C. After purification and recrystallization in different solvents the very soluble and stable title compounds have been isolated and structurally characterized. In {Li(L)}₂(μ‐pc)], the Li atom lies in a distorted tetragonal pyramid of four isoindole N atoms (N_i) at a distance varying between 2.163(5) and 2.301(5) Å, and an O atom at 1.863(5) Å. In Li(L)₄] · Lipc] · S, the Li atom of the cation coordinates four O atoms in a distorted tetrahedral arrangement at a distance varying from 1.887(9) to 1.953(9) Å, while the Li atom of the anion is in a quasi quadratic planar geometry of four N_i atoms (1.951(9)–1.977(9) Å) with the Li atom being displaced by 0.15 Å out of the (N_i)₄ plane. The structural data of the distorted tetragonal pyramidale Mg(N_i)₄O moiety in Mg(L)pc] and the solvates Mg(L)pc] · S (S = CH₂Cl₂, thf, 2py) generally do not vary significantly: Mg–N_i/2.035(3) –2.061(3) Å, Mg–O/1.955(2)–2.000(3) Å. The Mg atom is displaced by ca. 0.52 Å out of the (N_i)₄ plane towards the O atom and the Mg–O–P moiety is bent (ca. 153°). Zn(L)pc] · S crystallizes as a mixed crystal of equal parts of the conformer with a bent (155.1(3)°) and that of a quasi linear Zn–O–P moiety (174.2(3)°). Structural data of the Zn(N_i)₄O moiety: (Zn–N_i)_av: 2.024/2.013 Å; Zn–O: 2.050(4)/2.081(4) Å; Zn–(N_i)₄: 0.40/0.33 Å. In the crystal, the Mg and Zn derivates aggregate in double layers forming pairs. The pc ligands in the triclinic complexes with good overlap of the neighbouring pc ligands are in a waving conformation, while those in the monoclinic complexes with weak overlap are in a concave conformation.