The title compound 4 was synthesized from dipotassium 1,8‐anthracenedisulfonate (9) and potassium diphenylphosphide (Ph 2 PK). On reaction of 4 with nickel(II) chloride and bis‐(benzonitrile)palladium(II) chloride, cyclometallation of the C – H bond in anthracene 9‐position led to the square‐planar chelate complexes 11 and 13, respectively. In the case of the palladium complex 13, the cyclometallated structure was proved by X‐ray structure analysis. Treatment with aqueous potassium cyanide did not remove nickel from 11, but converted 11 into 12 by substitution of chloride with cyanide, demonstrating the high stability of these cyclometallated chelate complexes.