Dimer-of-dimers model for the oxygen-evolving complex of photosystem II. Synthesis and properties of [MnIV4O5(terpy)4(H2O)2](ClO4)6.

A dimer-of-dimers model compound for the oxygen-evolving complex of photosystem II, [[(H(2)O)(terpy)Mn(IV)(micro-O)(2)Mn(IV)(terpy)](2)(micro-O)](ClO(4))(6) (terpy = 2,2':6',2' '-terpyridine), has been prepared and characterized by X-ray crystallography and ESI-MS. Low pH was found to promote the disproportionation of [Mn(III/IV)(2)O(2)(terpy)(2)(OH(2))(2)](3+) to Mn(2+) and a Mn(IV/IV)(2)O(2)(terpy)(2) species; the latter complex slowly dimerizes to form the title complex. Protonation of a micro-oxo bridge is proposed to initiate the disproportionation, based on analogy with the [Mn(III/)(IV)(2)O(2)(bpy)(4)](3+) system.