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

作者：Goggins Eric M; Lekich Travis T; Weare Walter W^*; Sommer Roger D; Ribeiro Marcos A; Pinheiro Carlos B

来源：European Journal of Inorganic Chemistry, 2016, 2016(7): 1054-1059.

DOI：10.1002/ejic.201501325

• Heterometallic complexes
• Cyclic voltammetry
• Donor-acceptor systems
• Electronic structure
• Jahn-Teller distortion

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 degrees (Mn) to 170 degrees (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.

• 出版日期2016-3