Diorganodiphosphates (POP2−) and a triorgano‐methylenediphosphonate (PCP−) have been combined with zinc salts and the tridentate ligands L [L = bis(benzimidazolylmethyl)amine, bis(2‐pyridylmethyl)amine, triazacyclononane, trimethyltriazacyclononane, and (dimethylaminoethyl)(2‐pyridylmethyl)amine]. The resulting ternary complexes have been found to contain four‐, five‐, or six‐coordinate zinc. Four‐coordinate zinc has been identified in the complex types [L·Zn(PCP)]+ and [L·Zn(POP)Zn·L]2+, containing monodentate phosphate ligands. Five‐coordinate zinc has been found in the complexes [L·Zn(POP)] with chelating diphosphate ligands. Six‐coordinate zinc has been observed in the complex type [L·Zn(POP)·H2O] containing chelating diphosphates and in the complex type [L·Zn(POP)]2 in which the diphosphates act as tridentate bridging ligands. In a few cases, hydrolytic cleavage of the diphosphates resulted in the isolation of the trinuclear complexes [(L·Zn)3(ROPO3)2] HPO4 containing triply‐bridging monophosphates.
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