Issue 17, 2016

σ-Aromaticity in polyhydride complexes of Ru, Ir, Os, and Pt

Abstract

Transition-metal hydrides represent a unique class of compounds, which are essential for catalysis, organic synthesis, and hydrogen storage. In this work we study IrH5(PPh3)2, (RuH5(PiPr3)2), (OsH5(PiPr3)2), and OsH4(PPhMe2)3 polyhydride complexes, inspired by the recent discovery of the σ-aromatic PtZnH5 cluster anion. The distinctive feature of these molecules is that, like in the PtZnH5 cluster, the metal is five-fold coordinated in-plane, and holds additional ligands at the axial positions. This work shows that the unusual coordination in these compounds indeed can be explained by σ-aromaticity in the pentagonal arrangement, stabilized by the atomic orbitals on the metal. Based on this newly elucidated bonding principle, we additionally propose a new family of polyhydrides that display a uniquely high coordination. We also report the first indications of how aromaticity may impact the reactivity of these molecules.

Graphical abstract: σ-Aromaticity in polyhydride complexes of Ru, Ir, Os, and Pt

Supplementary files

Article information

Article type
Paper
Submitted
23 7 2015
Accepted
17 9 2015
First published
17 9 2015

Phys. Chem. Chem. Phys., 2016,18, 11644-11652

Author version available

σ-Aromaticity in polyhydride complexes of Ru, Ir, Os, and Pt

E. Jimenez-Izal and A. N. Alexandrova, Phys. Chem. Chem. Phys., 2016, 18, 11644 DOI: 10.1039/C5CP04330A

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