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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.

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Figure 1: Synthesis and transformations of the Y4M (M = Mo, W) heteropentametallic polyhydrides (Cp* = C5Me5, Cp′ = C5Me4SiMe3).
Figure 2: X-ray and neutron structures of the heterometallic polyhydrides with 30% thermal ellipsoids.
Figure 3: X-ray monitoring of hydrogenation of 5 to give 3a in a single-crystal to single-crystal process.
Figure 4: DFT-calculated energy profile for hydrogenation of 5m (a model of 5).

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Acknowledgements

This work is dedicated to the memory of Professor Robert Bau (1944–2008). We are grateful to K. Aznavour for her assistance in initial neutron diffraction studies, to the Institut Laue-Langevin for the allocations of beam time on D19 and VIVALDI for the neutron studies quoted here of 2b and 3b , respectively, and to D. Hashizume for help with analysis of the neutron data of 3b . This work was supported by a Grant-in-Aid for Young Scientists (B) (no. 21750068), a Grant-in-Aid for Scientific Research (S) (no. 21225004) from JSPS, National Natural Science Foundation of China (no. 21028001), RICC (RIKEN Integrated Cluster of Clusters), and the Network and Information Centre of Dalian University of Technology for computational resources. Z.H. is grateful to the Chang Jiang Scholar Program for Visiting Professor.

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Authors

Contributions

T. Shima carried out all syntheses, NMR and X-ray characterizations, and reactivity studies. Y.L. carried out DFT calculations. T. Stewart, R.B., G.J.M. and S.A.M. carried out neutron diffraction studies. Z.H. directed the project. T. Shima and Z.H. analysed the data and wrote the manuscript.

Corresponding author

Correspondence to Zhaomin Hou.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 5015 kb)

Supplementary information

Crystallographic data for compound 2a (CIF 37 kb)

Supplementary information

Crystallographic data data for compound 2b (CIF 39 kb)

Supplementary information

Neutron diffraction for compound 2b (CIF 65 kb)

Supplementary information

Crystallographic data for compound 3a (CIF 36 kb)

Supplementary information

Crystallographic data data for compound 3b (CIF 36 kb)

Supplementary information

Neutron diffraction for compound 3b (CIF 54 kb)

Supplementary information

Crystallographic data for compound 4 (CIF 35 kb)

Supplementary information

Crystallographic data for compound 5 (CIF 37 kb)

Supplementary information

Crystallographic data for compound 3a_Dy (CIF 37 kb)

Supplementary information

Crystallographic data for compound 5_Dy (CIF 37 kb)

Supplementary information

Crystallographic data for compound 3a_Ho (CIF 43 kb)

Supplementary information

Crystallographic data for compound 5_Ho (CIF 38 kb)

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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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