True boundary for the formation of homoleptic transition-metal hydride complexes

Angewandte Chemie
Shigeyuki TakagiShin-ichi Orimo

Abstract

Despite many exploratory studies over the past several decades, the presently known transition metals that form homoleptic transition-metal hydride complexes are limited to the Groups 7-12. Here we present evidence for the formation of Mg3 CrH8 , containing the first Group 6 hydride complex [CrH7 ](5-) . Our theoretical calculations reveal that pentagonal-bipyramidal H coordination allows the formation of σ-bonds between H and Cr. The results are strongly supported by neutron diffraction and IR spectroscopic measurements. Given that the Group 3-5 elements favor ionic/metallic bonding with H, along with the current results, the true boundary for the formation of homoleptic transition-metal hydride complexes should be between Group 5 and 6. As the H coordination number generally tends to increase with decreasing atomic number of transition metals, the revised boundary suggests high potential for further discovery of hydrogen-rich materials that are of both technological and fundamental interest.

References

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Citations

Mar 14, 2017·Scientific Reports·Shigeyuki TakagiShin-Ichi Orimo
Jul 12, 2017·ACS Combinatorial Science·Natacha BourgeoisJean-Marc Joubert
Dec 24, 2018·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Toyoto SatoShin-Ichi Orimo
Dec 27, 2017·Inorganic Chemistry·Toyoto SatoShin-Ichi Orimo
Aug 1, 2019·Inorganic Chemistry·Kristina SpektorUlrich Häussermann
Oct 3, 2018·Chemical Reviews·Andreas SchneemannVitalie Stavila
Mar 7, 2020·Inorganic Chemistry·Takeshi YajimaZenji Hiroi
Nov 4, 2020·Inorganic Chemistry·Kristina SpektorUlrich Häussermann

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