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Heterometallic Polyhydride Complexes Containing Yttrium Hydrides with Different Cp Ligands: Synthesis, Structure, and Hydrogen-Uptake/Release Properties

Authors

  • Dr. Takanori Shima,

    1. Organometallic Chemistry Laboratory and Advanced Catalyst Research Team, RIKEN Advanced Science Institute, Hirosawa 2-1, Wako, Saitama 351-0198 (Japan), Fax: (+81) 48-462-4665
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  • Prof. Dr. Zhaomin Hou

    Corresponding author
    1. Organometallic Chemistry Laboratory and Advanced Catalyst Research Team, RIKEN Advanced Science Institute, Hirosawa 2-1, Wako, Saitama 351-0198 (Japan), Fax: (+81) 48-462-4665
    • Organometallic Chemistry Laboratory and Advanced Catalyst Research Team, RIKEN Advanced Science Institute, Hirosawa 2-1, Wako, Saitama 351-0198 (Japan), Fax: (+81) 48-462-4665

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Abstract

A new family of Y4/M2 and Y5/M heterobimetallic rare-earth-metal/d-block-transition-metal[BOND]polyhydride complexes has been synthesized. The reactions of the tetranuclear yttrium[BOND]octahydride complex [{Cp′′Y(μ-H)2}4(thf)4] (Cp′′=C5Me4H, 1-C5Me4H) with one equivalent of Group-6-metal[BOND]pentahydride complexes [Cp*M(PMe3)H5] (M=Mo, W; Cp*=C5Me5) afforded pentanuclear heterobimetallic Y4/M[BOND]polyhydride complexes [{(Cp′′Y)4(μ-H)7}(μ-H)4MCp*(PMe3)] (M=Mo (2 a), W (2 b)). UV irradiation of compounds 2 a,b in THF gave PMe3-free complexes [{(Cp′′Y)4(μ-H)6(thf)2}(μ-H)5MCp*] (M=Mo (3 a), W (3 b)). Compounds 3 a,b reacted with one equivalent of [Cp*M(PMe3)H5] to afford hexanuclear Y4/M2 complexes [{Cp*M(μ-H)5}{(Cp′′Y)4(μ-H)5}{(μ-H)4MCp*(PMe3)}] (M=Mo (4 a), W (4 b)). UV irradiation of compounds 4 a,b provided the PMe3-free complexes [(Cp′′Y)4(μ-H)4{(μ-H)5MCp*}2] (M=Mo (5 a), W (5 b)). C5Me4Et-ligated analogue [(Cp′′Y)4(μ-H)4{(μ-H)5Mo(C5Me4Et)}2] (5 a′) was obtained from the reaction of 1-C5Me4H with [(C5Me4Et)Mo(PMe3)H5]. On the other hand, the reaction of pentanuclear yttrium[BOND]decahydride complex [{(C5Me4R)Y(μ-H)2}5(thf)2] (1-C5Me5: R=Me; 1-C5Me4Et: R=Et) with [Cp*M(PMe3)H5] gave the hexanuclear heterobimetallic Y5/M[BOND]polyhydride complexes [({(C5Me4R)Y}5(μ-H)8)(μ-H)5MCp*] (6 a: M=Mo, R=Me; 6 a′: M=Mo, R=Et; 6 b: M=W, R=Me). Compound 5 a released two molecules of H2 under vacuum to give [(Cp′′Y)4(μ-H)2{(μ-H)4MoCp*}2] (7). In contrast, compound 6 a lost one molecule of H2 under vacuum to yield [{(Cp*Y)5(μ-H)7}(μ-H)4MoCp*] (8). Both compounds 7 and 8 readily reacted with H2 to regenerate compounds 5 a and 6 a, respectively. The structures of compounds 4 a, 5 a′, 6 a′, 7, and 8 were determined by single-crystal X-ray diffraction.

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