Organometallic Chemistry Laboratory and Advanced Catalyst Research Team, RIKEN Advanced Science Institute, Hirosawa 2-1, Wako, Saitama 351-0198, Japan.
Chemistry. 2013 Mar 4;19(10):3458-66. doi: 10.1002/chem.201203495. Epub 2013 Jan 17.
A new family of Y(4)/M(2) and Y(5)/M heterobimetallic rare-earth-metal/d-block-transition-metal-polyhydride complexes has been synthesized. The reactions of the tetranuclear yttrium-octahydride complex [{Cp''Y(μ-H)(2)}(4)(thf)(4)] (Cp'' = C(5)Me(4)H, 1-C(5)Me(4)H) with one equivalent of Group-6-metal-pentahydride complexes [CpM(PMe(3))H(5)] (M = Mo, W; Cp = C(5)Me(5)) afforded pentanuclear heterobimetallic Y(4)/M-polyhydride complexes [{(Cp''Y)(4)(μ-H)(7)}(μ-H)(4)MCp*(PMe(3))] (M = Mo (2 a), W (2 b)). UV irradiation of compounds 2 a,b in THF gave PMe(3)-free complexes [{(Cp''Y)(4)(μ-H)(6)(thf)(2)}(μ-H)(5)MCp*] (M = Mo (3 a), W (3 b)). Compounds 3 a,b reacted with one equivalent of [CpM(PMe(3))H(5)] to afford hexanuclear Y(4)/M(2) complexes [{CpM(μ-H)(5)}{(Cp''Y)(4)(μ-H)(5)}{(μ-H)(4)MCp*(PMe(3))}] (M = Mo (4 a), W (4 b)). UV irradiation of compounds 4 a,b provided the PMe(3)-free complexes [(Cp''Y)(4)(μ-H)(4){(μ-H)(5)MCp*}(2)] (M = Mo (5 a), W (5 b)). C(5)Me(4)Et-ligated analogue [(Cp''Y)(4)(μ-H)(4){(μ-H)(5)Mo(C(5)Me(4)Et)}(2)] (5 a') was obtained from the reaction of 1-C(5)Me(4)H with [(C(5)Me(4)Et)Mo(PMe(3))H(5)]. On the other hand, the reaction of pentanuclear yttrium-decahydride complex [{(C(5)Me(4)R)Y(μ-H)(2)}(5)(thf)(2)] (1-C(5)Me(5): R = Me; 1-C(5)Me(4)Et: R = Et) with [CpM(PMe(3))H(5)] gave the hexanuclear heterobimetallic Y(5)/M-polyhydride complexes [({(C(5)Me(4)R)Y}(5)(μ-H)(8))(μ-H)(5)MCp] (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 H(2) under vacuum to give [(Cp''Y)(4)(μ-H)(2){(μ-H)(4)MoCp*}(2)] (7). In contrast, compound 6 a lost one molecule of H(2) under vacuum to yield [{(CpY)(5)(μ-H)(7)}(μ-H)(4)MoCp] (8). Both compounds 7 and 8 readily reacted with H(2) 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.
一种新的 Y(4)/M(2) 和 Y(5)/M 异双核稀土金属/d 区过渡金属多氢化物配合物家族已经被合成。四聚体钇八氢化物配合物[{Cp''Y(μ-H)(2)}(4)(thf)(4)] (Cp'' = C(5)Me(4)H, 1-C(5)Me(4)H)与等摩尔的第六族金属五氢化物配合物[CpM(PMe(3))H(5)] (M = Mo, W; Cp = C(5)Me(5))反应，得到五核异双核 Y(4)/M-多氢化物配合物[{(Cp''Y)(4)(μ-H)(7)}(μ-H)(4)MCp*(PMe(3))] (M = Mo (2 a), W (2 b))。化合物 2 a,b 在 THF 中的紫外光照射得到无 PMe(3)的配合物[{(Cp''Y)(4)(μ-H)(6)(thf)(2)}(μ-H)(5)MCp*] (M = Mo (3 a), W (3 b))。化合物 3 a,b 与等摩尔的[CpM(PMe(3))H(5)]反应，得到六核 Y(4)/M(2)配合物[{CpM(μ-H)(5)}{(Cp''Y)(4)(μ-H)(5)}{(μ-H)(4)MCp*(PMe(3))}] (M = Mo (4 a), W (4 b))。化合物 4 a,b 的紫外光照射提供了无 PMe(3)的配合物[(Cp''Y)(4)(μ-H)(4){(μ-H)(5)MCp*}(2)] (M = Mo (5 a), W (5 b))。C(5)Me(4)Et 配体类似物[(Cp''Y)(4)(μ-H)(4){(μ-H)(5)Mo(C(5)Me(4)Et)}(2)] (5 a')是由 1-C(5)Me(4)H 与[(C(5)Me(4)Et)Mo(PMe(3))H(5)]反应得到的。另一方面，五核钇十氢化物配合物[{(C(5)Me(4)R)Y(μ-H)(2)}(5)(thf)(2)] (1-C(5)Me(5): R = Me; 1-C(5)Me(4)Et: R = Et)与[CpM(PMe(3))H(5)]反应得到异双核 Y(5)/M-多氢化物配合物[({(C(5)Me(4)R)Y}(5)(μ-H)(8))(μ-H)(5)MCp] (6 a: M = Mo, R = Me; 6 a': M = Mo, R = Et; 6 b: M = W, R = Me)。化合物 5 a 在真空中释放出两个分子的 H(2)，得到[(Cp''Y)(4)(μ-H)(2){(μ-H)(4)MoCp*}(2)] (7)。相比之下，化合物 6 a 在真空中失去一个分子的 H(2)，生成[{(CpY)(5)(μ-H)(7)}(μ-H)(4)MoCp] (8)。化合物 7 和 8 都容易与 H(2)反应，分别再生化合物 5 a 和 6 a。化合物 4 a、5 a'、6 a'、7 和 8 的结构通过单晶 X 射线衍射确定。
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