Heterometallic Polyhydride Complexes Containing Yttrium Hydrides with Different Cp Ligands: Synthesis, Structure, and Hydrogen-Uptake/Release Properties
Heterometallic Polyhydride Complexes Containing Yttrium Hydrides with Different Cp Ligands: Synthesis, Structure, and Hydrogen-Uptake/Release Properties
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含有不同 Cp 配体的氢化钇的异金属多氢化物配合物：合成、结构和氢吸收/释放性能
DOI：
10.1002/chem.201203495
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
T. Shima and Z. Hou
中科院分区：
文献类型：
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作者：
S.Inagaki;et al;藤原治;池谷和信;柴山義行;鳥居祥二;佐藤隆広(編著);岩田久人・金恩英;Takafumi Hirata;村田憲一郎・田中肇;T. Shima and Z. Hou
A new family of Y4/M2and Y5/M heterobimetallic rare‐earth‐metal/d‐block‐transition‐metalpolyhydride complexes has been synthesized. The reactions of the tetranuclear yttriumoctahydride complex [{Cp′′Y(μ‐H)2}4(thf)4] (Cp′′=C5Me4H,1‐C5Me4H) with one equivalent of Group‐6‐metalpentahydride complexes [Cp*M(PMe3)H5] (M=Mo, W; Cp*=C5Me5) afforded pentanuclear heterobimetallic Y4/Mpolyhydride complexes [{(Cp′′Y)4(μ‐H)7}(μ‐H)4MCp*(PMe3)] (M=Mo (2 a), W (2 b)). UV irradiation of compounds2 a,bin THF gave PMe3‐free complexes [{(Cp′′Y)4(μ‐H)6(thf)2}(μ‐H)5MCp*] (M=Mo (3 a), W (3 b)). Compounds3 a,breacted with one equivalent of [Cp*M(PMe3)H5] to afford hexanuclear Y4/M2complexes [{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 compounds4 a,bprovided 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 of1‐C5Me4Hwith [(C5Me4Et)Mo(PMe3)H5]. On the other hand, the reaction of pentanuclear yttriumdecahydride 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/Mpolyhydride 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). Compound5 areleased two molecules of H2under vacuum to give [(Cp′′Y)4(μ‐H)2{(μ‐H)4MoCp*}2] (7). In contrast, compound6 alost one molecule of H2under vacuum to yield [{(Cp*Y)5(μ‐H)7}(μ‐H)4MoCp*] (8). Both compounds7and8readily reacted with H2to regenerate compounds5 aand6 a, respectively. The structures of compounds4 a,5 a′,6 a′,7, and8were determined by single‐crystal X‐ray diffraction.
A new family of Y4/M2and Y5/M heterobimetallic rare‐earth‐metal/d‐block‐transition‐metalpolyhydride complexes has been synthesized. The reactions of the tetranuclear yttriumoctahydride complex [{Cp′′Y(μ‐H)2}4(thf)4] (Cp′′=C5Me4H,1‐C5Me4H) with one equivalent of Group‐6‐metalpentahydride complexes [Cp*M(PMe3)H5] (M=Mo, W; Cp*=C5Me5) afforded pentanuclear heterobimetallic Y4/Mpolyhydride complexes [{(Cp′′Y)4(μ‐H)7}(μ‐H)4MCp*(PMe3)] (M=Mo (2 a), W (2 b)). UV irradiation of compounds2 a,bin THF gave PMe3‐free complexes [{(Cp′′Y)4(μ‐H)6(thf)2}(μ‐H)5MCp*] (M=Mo (3 a), W (3 b)). Compounds3 a,breacted with one equivalent of [Cp*M(PMe3)H5] to afford hexanuclear Y4/M2complexes [{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 compounds4 a,bprovided 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 of1‐C5Me4Hwith [(C5Me4Et)Mo(PMe3)H5]. On the other hand, the reaction of pentanuclear yttriumdecahydride 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/Mpolyhydride 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). Compound5 areleased two molecules of H2under vacuum to give [(Cp′′Y)4(μ‐H)2{(μ‐H)4MoCp*}2] (7). In contrast, compound6 alost one molecule of H2under vacuum to yield [{(Cp*Y)5(μ‐H)7}(μ‐H)4MoCp*] (8). Both compounds7and8readily reacted with H2to regenerate compounds5 aand6 a, respectively. The structures of compounds4 a,5 a′,6 a′,7, and8were determined by single‐crystal X‐ray diffraction.