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True Boundary for the Formation of Homoleptic Transition‐Metal Hydride Complexes
Author(s) -
Takagi Shigeyuki,
Iijima Yuki,
Sato Toyoto,
Saitoh Hiroyuki,
Ikeda Kazutaka,
Otomo Toshiya,
Miwa Kazutoshi,
Ikeshoji Tamio,
Aoki Katsutoshi,
Orimo Shinichi
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201500792
Subject(s) - homoleptic , hydride , chemistry , transition metal , crystallography , main group element , ionic bonding , neutron diffraction , metal , pentagonal bipyramidal molecular geometry , inorganic chemistry , catalysis , crystal structure , ion , organic chemistry
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 Mg 3 CrH 8 , containing the first Group 6 hydride complex [CrH 7 ] 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.