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Finally Stable and Homoleptic: Isolation and Characterization of {Cu[Fe(CO)5]2}+ Stabilized with Perfluoroalkoxyaluminate Anion, [Al(OC(CF3)3)4]− by Vadim Zhuravlev; Przemysław J. Malinowski is a Chemistry article available to read on EtoBox.

What is Finally Stable and Homoleptic: Isolation and Characterization of {Cu[Fe(CO)5]2}+ Stabilized with Perfluoroalkoxyaluminate Anion, [Al(OC(CF3)3)4]− about?

Developments in the chemistry of weakly coordinating anions enabled isolation of numerous unique metal complexes with unusual ligands. An important example is the family of metal-Fe(CO)5 complexes. In the current paper we present synthesis and thorough characterization of the first truly homoleptic {Cu[Fe(CO)5]2} + cation obtained as a salt of weakly coordinating [Al(OR F )4] − (R F =C(CF3)3) anion. TGA/DSC/MS study show that its decomposition becomes noticeable only above 110°C, thus it can be stored as powder in air-free conditions for months. The crystal structure of {Cu[Fe(CO)5]2} + shows strong asymmetry of the cation and very short Cu-CO bonds in comparison to analogous {M[Fe(CO)5]2} + where M = Ag or Au. Characterization is complemented with analysis of vibrational spectra and extensive DFT calculations which give insight into the energetics of Cu + -Fe(CO)5 systems. Our results show that {Cu[Fe(CO)5]2} + is homoleptic only as salt of [Al(OR F )4] − . Furthermore, in the presence of additional, even weakly basic ligands, the Cu + -Fe(CO)5 bond strength decreases what may contribute to the complex's instability in liquid SO2 or in the presence of [SbF6] − . These conclusions

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Author

Vadim Zhuravlev; Przemysław J. Malinowski

Publisher

Wiley

Published

2023

Language

EN

Field

Chemistry (Physical Sciences)