Magnesium phthalocyanines: Synthesis and properties of halophthalocyaninatomagnesate, [Mg(X)Pc(2-)](-) (X=F, Cl, Br); Crystal structure of bis(triphenylphosphine)iminiumchloro-(phthalocyaninato)magnesate acetone solvate

Magnesium phthalocyanine reacts with excess tetra(n-butyl)ammonium- or bis(triphenylphosphine)iminiumhalide (((n)Bu(4)N)X or (PNP)X; X = F, Cl, Br) yielding halophthalocyaninatomagnesate ([Mg(X)Pc(2-)](-); X = F, Cl, Br), which crystallizes in part as a scarcely soluble ((n)Bu(4)N) or (PNP) complex-salt. Single-crystal X-ray diffraction analysis of (b)(PNP)[Mg(Cl)Pc(2-)] . CH3COCH3 reveals that the Mg atom has a tetragonal pyramidal coordination geometry with the Mg atom displaced out of the center (Ct) of the inner nitrogen atoms (N-iso) of the nonplanar Pc ligand toward the Cl atom (d(Mg-Ct)= 0.572(3) Angstrom; d(Mg-Cl) = 2.367(2) Angstrom). The average Mg-N-iso distance is 2.058 Angstrom. Pairs of partially overlapping anions are present. The cation adopts a bent conformation ((b)(PNP)(+): d(P1-N(K))= 1.568(3) Angstrom; d(P2-N(K)) = 1.587(3) Angstrom; less than with right parenthesis(P1-N(K)-P2) = 141.3(2)degrees). Electrochemical and spectroscopic properties are discussed.