Synthesis and crystal structures of a family of bimetallic complexes with phenyl-substituted bridging tetraoxolene ligands

苯基取代桥联四氧戊烯配体的双金属配合物的合成与晶体结构

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Abstract

Seven dinuclear metal complexes and one trinuclear metal complex have been synthesized using the redox-active diphenyl-substituted tetraoxolene 2,5-dihydroxy-3,6-diphenyl-1,4-benzoquinone (H(2)Ph(2)dhbq, C(18)H(12)O(4)) as a bridging ligand and tris[(pyridin-2-yl)methyl]amine (TPA, C(18)H(18)N(4)) as a tetradentate terminal ligand. Single-crystal X-ray diffraction data confirm the final redox states of all components, revealing both expected and unexpected redox behavior across the eight reported complexes. Metal complexes with the formula [M(II)(2)(Ph(2)dhbq(2-))(TPA)(2)](2+) can be synthesized from Mn, Fe, Co, Ni, Zn, and Ru, using either the oxidized ligand H(2)Ph(2)dhbq or a combination of the reduced ligand H(4)Ph(2)dhbq and an in-situ oxidant. Additionally, switching to Group 13 elements, such as Ga, facilitates the formation of the related [M(III)(2)(Ph(2)dhbq(4-))(TPA)(2)](2+) complex, wherein the ligand remains in its initial reduced state.

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