A Periodic Walk through a Series of First‐Row, Oxido‐Bridged, Heterodimetallic Molecules: Synthesis and Structure

A series of heterodimetallic molecules, centered around an LTi=OM2+L′ (M = Mn, Fe, Co, Ni, Cu, Zn) core, are described. Each of these complexes are structurally similar, with L = tmtaa and L′ = Py5Me2. The Ti=OM linkage is slightly bent, varying from 157° (Mn) to 170° (Zn), with bond lengths typical of a dative bond between the Ti=O group and the M2+ center. The relative strength of the heterodimetallic linkage is correlated with the Lewis acidity of the M2+ precursor, with Mn2+ showing the strongest interaction and Ni2+ the weakest. By varying the metal identity the electrochemical properties of the molecules can be tuned, along with the M3+/2+ redox couple. This series of complexes provide a platform for studying structure/function relationships in heterodimetallic molecules linked through a single atom. For instance, spectroscopic features such as IR stretching frequencies can be roughly correlated with structural features such as bond lengths and angles.

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