Peroxo(tetraphenylporphinato)manganese(iii) and chloro(tetraphenylporphinato)manganese(ii) anions. synthesis, crystal structures, and electronic structures.

The syntheses and X-ray crystal structures of potassium cryptate (K(K222))/sup +/ salts of the (chlorotetraphenyl-porphinato)manganese(II) and (peroxotetraphenylporphinato)manganese(III) anions are reported. The complexes are prepared in THF by reaction of Mn/sup II/TPP with Cl/sup -/ and O/sub 2//sup -/, respectively. Both complexes crystallize in the space group P2/sub 1//c with four formula units per unit cell. The unit cell of the chloride complex has dimensions a = 12.834 A, b = 18.999 A, c = 23.313 A, ..beta.. = 99.02 at 133 K. The manganese is pentacoordinate, bonded to four pyrrole nitrogens and a chloride ion. The manganese atom is displaced 0.641 A from the least-squares plan based on the four pyrrole nitrogen atoms in the direction of the chloride ligand. The unit cell of the manganese(III)-peroxo complex has dimensions a = 12.895 A, b = 18.836 A, c = 23.045 A, ..beta.. = 99.17 at 133 K. The manganese is bonded to four pyrrole nitrogens and the bidentate peroxo ligand. The manganese lies 0.764 A above the least-squares plane based on the pyrrole nitrogens toward the peroxo ligand. The O-O bond distance is 1.421 A, and the Mn-O distances are 1.901 and 1.888 A. The peroxo ligand is bound side-onmore » to the manganese, eclipsing two of the manganese-pyrrole nitrogen bonds.« less