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Journal Article

Structure and Properties of a Five-Coordinate Nickel(II) Porphyrin

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Levin Rojas,  Natalia
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

Gutzeit, F., Dommaschk, M., Levin Rojas, N., Buchholz, A., Schaub, E., Plass, W., et al. (2019). Structure and Properties of a Five-Coordinate Nickel(II) Porphyrin. Inorganic Chemistry, 58(19), 12542-12546. doi:10.1021/acs.inorgchem.9b00348.


Cite as: https://hdl.handle.net/21.11116/0000-0005-DDB6-5
Abstract
Axial coordination in nickel(II) porphyrins has been thoroughly investigated and is well understood. However, isolated five-coordinate nickel(II) porphyrins are still elusive after 50 years of intense research, even though they play a crucial role as intermediates in enzymes and catalysts. Herein we present the first fully stable, thoroughly characterized five-coordinate nickel(II) porphyrin in solution and in the solid state (crystal structure). The spectroscopic properties indicate pure high-spin behavior (S = 1). There are distinct differences in the NMR, UV-vis, and redox behavior compared to those of high-spin six-coordinate [with two axial ligands, such as NiTPPF10 center dot(py)(2)] and low-spin fourcoordinate (NiTPPF10) nickel(II) porphyrins. The title compound, a strapped nickel(II) porphyrin, allows a direct comparison of four-, five-, and six-coordinate nickel(II) porphyrins, depending on the environment. With this reference in hand, previous results were reevaluated, for example, the switching efficiencies and thermodynamic data of nickel(II) porphyrin-based spin switches in solution.