Molecular heterometallic hydride clusters composed of rare-earth and d-transition metals

Abstract

Heteromultimetallic hydride clusters containing both rare-earth and d-transition metals are of interest in terms of both their structure and reactivity. However, such heterometallic complexes have not yet been investigated to a great extent because of difficulties in their synthesis and structural characterization. Here, we report the synthesis, X-ray and neutron diffraction studies, and hydrogen addition and release properties of a family of rare-earth/d-transition-metal heteromultimetallic polyhydride complexes of the core structure type ‘Ln4MHn’ (Ln = Y, Dy, Ho; M = Mo, W; n = 9, 11, 13). Monitoring of hydrogen addition to a hydride cluster such as [{(C5Me4SiMe3)Y}4(μ-H)9Mo(C5Me5)] in a single-crystal to single-crystal process by X-ray diffraction has been achieved for the first time. Density functional theory studies reveal that the hydrogen addition process is cooperatively assisted by the Y/Mo heteromultimetallic sites, thus offering unprecedented insight into the hydrogen addition and release process of a metal hydride cluster. Well-defined molecular polyhydrides composed of two substantially different types of metals — such as rare-earth and d transition metals — are interesting both in terms of structure and potential properties, but have been largely unexplored so far. Now, a series of such hydride clusters are reported and are found to exhibit unprecedented structural features as well as unique hydrogen addition and release properties.

Cite this article

Shima, T., Luo, Y., Stewart, T. et al. Molecular heterometallic hydride clusters composed of rare-earth and d-transition metals. Nature Chem 3, 814–820 (2011). https://doi.org/10.1038/nchem.1147

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