title: 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 'Ln(4)MH(n)' (Ln = Y, Dy, Ho; M = Mo, W; n = 9, 11, 13). Monitoring of hydrogen addition to a hydride cluster such as [{(C(5)Me(4)SiMe(3))Y}(4)(μ-H)(9)Mo(C(5)Me(5))] 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.
authors.affiliation: Organometallic Chemistry Laboratory and Advanced Catalyst Research Team, RIKEN Advanced Science Institute, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
authors.forename: Takanori
authors.initials: T
authors.lastname: Shima
authors.forename: Yi
authors.initials: Y
authors.lastname: Luo
authors.forename: Timothy
authors.initials: T
authors.lastname: Stewart
authors.forename: Robert
authors.initials: R
authors.lastname: Bau
authors.forename: Garry J
authors.initials: GJ
authors.lastname: McIntyre
authors.forename: Sax A
authors.initials: SA
authors.lastname: Mason
authors.forename: Zhaomin
authors.initials: Z
authors.lastname: Hou
mesh_terms: D018360:Crystallography, X-Ray; D006859:Hydrogen / Q000737:chemistry*; D006865:Hydrogenation; D008674:Metals, Rare Earth / Q000737:chemistry*; D008968:Molecular Conformation; D033363:Neutron Diffraction; D013816:Thermodynamics; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D008674:Metals, Rare Earth; D028561:Transition Elements; D006859:Hydrogen