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

2016; Wiley; Volume: 2016; Issue: 7 Linguagem: Inglês

10.1002/ejic.201501325

1099-0682

Eric M. Goggins, Travis T. Lekich, Walter W. Weare, Roger D. Sommer, Marcos A. Ribeiro, Carlos B. Pinheiro,

Porphyrin and Phthalocyanine Chemistry

Abstract A series of heterodimetallic molecules, centered around an LTi=O→M 2+ L′ (M = Mn, Fe, Co, Ni, Cu, Zn) core, are described. Each of these complexes are structurally similar, with L = tmtaa and L′ = Py 5 Me 2 . The Ti=O→M 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 M 2+ center. The relative strength of the heterodimetallic linkage is correlated with the Lewis acidity of the M 2+ precursor, with Mn 2+ showing the strongest interaction and Ni 2+ the weakest. By varying the metal identity the electrochemical properties of the molecules can be tuned, along with the M 3+/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.