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Issue 17, 2016
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σ-Aromaticity in polyhydride complexes of Ru, Ir, Os, and Pt

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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

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The article was received on 23 Jul 2015, accepted on 17 Sep 2015 and first published on 17 Sep 2015


Article type: Paper
DOI: 10.1039/C5CP04330A
Author version available: Download Author version (PDF)
Citation: Phys. Chem. Chem. Phys., 2016,18, 11644-11652
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    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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