A novel triruthenium hydrido cluster, (Cp*Ru)₃(μ₃-H)(μ-H)₂(μ-CO) (4; Cp* = η⁵-C₅Me₅), having a bridging CO ligand was synthesized by the reaction of {Cp*Ru(μ-H)}₃(μ₃-O) (3) with methanol. Upon introduction of a CO ligand, the cyclic voltammogram of 4 demonstrated a significant shift of the redox potential in the positive direction in comparison to a pentahydrido complex, {Cp*Ru(μ-H)}₃(μ₃-H)₂ (1), which adopts the same 44-electron configuration. Owing to its coordinatively unsaturated nature, 4 readily reacted with butadiene, terminal alkynes, and alkenes similarly to the parent pentahydrido complex 1. However, the reactivity was slightly different from that of 1, and the influence of the CO ligand at the triruthenium site was evaluated by the reaction of various unsaturated hydrocarbons. The reaction of 4 with 1,3-dienes yielded a diene adduct, {Cp*Ru(μ-H)}₃(μ-η²:η²-s-cis-H₂C═CRCH═CH₂)(CO) (5a, R = H; 5b, R = Me) without elimination of dihydrogen. In the same manner as for 1, 4 reacted with phenylacetylene to yield a μ₃-η²:η²(⊥)-alkyne complex, (Cp*Ru)₃(μ-H){μ₃-η²:η²(⊥)-PhCCH}(μ₃-CO) (7a); in contrast, an isomeric μ₃-pentenylidene complex, (Cp*Ru)₃(μ-H){μ₃-η²-C═C(nPr)H}(μ-CO) (9b), was obtained by reaction with 1-pentyne. A series of products was obtained by the reaction of 4 with ethylene molecules. A μ₃-ethylidyne complex, (Cp*Ru)₃(μ-H)₂(μ₃-CMe)(μ-CO) (11), was initially formed, accompanied by the formation of ethane at ambient temperature. The treatment of 11 with ethylene resulted in the removal of hydrido ligands, affording a μ₃-vinylidene complex, (Cp*Ru)₃(μ-H)(μ₃-η²-C═CH₂)(μ-CO) (9a). At higher temperatures, a second ethylene molecule was incorporated in the triruthenium plane and an equilibrated mixture of a μ₃-ethylidyne−μ-ethylidyne complex, (Cp*Ru)₃(μ-H)(μ-CMe)(μ₃-CMe)(μ-CO) (13), and μ₃-ethylidyne−μ-vinyl complex, (Cp*Ru)₃(μ-H)(μ₃-CMe)(μ-η²-CH═CH₂)(μ-CO) (12), was obtained. The formation of a μ₃-η³-C₃ ring on the Ru₃ plane was observed upon the thermolysis of the equilibrated mixture at 180 °C, which clearly demonstrates the coupling of the two C₂ moieties placed on each face of the triruthenium plane.

中文翻译：

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具有桥联羰基配体的电子不足的三氢化铀氢配合物的合成：CO配体对氢簇的性质和反应性的影响

一种新颖的三钌氢基簇，（CP * Ru）的₃（μ ₃ -H）（μ-H）₂（μ-CO）（4 ;的Cp * =η ⁵ -C ₅我₅），其具有桥联配体CO是由{的Cp *茹（μ-H）}的反应合成₃（μ ₃ -O）（3）用甲醇。当引入一个CO配体，的循环伏安图4展示了在正方向上的氧化还原电位的相比于pentahydrido复杂，{的Cp *茹（μ-H）}一显著移位₃（μ ₃ -H）₂（1个），采用相同的44电子结构。由于其配位的不饱和性质，4容易与丁二烯，末端炔烃和烯烃反应，类似于母体五氢络合物1。但是，反应性与1的反应性略有不同，并且通过各种不饱和烃的反应评价了CO配体在三钌位点的影响。的反应4与1,3-二烯得到的二烯加合物，{的Cp *茹（μ-H）} ₃（μ-η ²：η ² -小号-顺-H ₂ C═CRCH═CH ₂）（CO ）（5a，R = H; 5b，R ＝ Me）而没有消除二氢。以相同的方式作为1，4与苯基反应以产生一个μ ₃ -η ²：η ²（⊥）-alkyne络合物，（CP * Ru）的₃（μ-H）{μ ₃ -η ²：η ²（⊥）-PhCCH}（μ ₃ -CO）（图7a）; 与此相反，异构μ ₃ -pentenylidene络合物，（CP * Ru）的₃（μ-H）{μ ₃ -η ² -C═C（Ñ PR）H}（μ-CO）（图9b），通过获得与1-戊炔反应。通过4的反应获得了一系列产物与乙烯分子。甲μ ₃ -ethylidyne络合物，（CP * Ru）的₃（μ-H）₂（μ ₃ -CMe）（μ-CO）（11）中，最初形成的，伴随着在环境温度下的形成的乙烷。治疗11与乙烯，并因此删除氢基配位体，得到一个μ ₃ -vinylidene络合物，（CP * Ru）的₃（μ-H）（μ ₃ -η ² -C═CH ₂）（μ-CO） （9a）。在较高温度下，第二乙烯分子中的三钌平面被合并和μ的平衡混合物₃ -ethylidyne-μ-乙川络合物，（CP * Ru）的₃（μ-H）（μ-CME）（μ ₃ -CMe）（μ-CO）（13），和μ ₃ -ethylidyne-μ-乙烯基络合物，（CP * Ru）的₃（μ-H）（μ ₃ -CMe）（μ-η ² -CH = CH ₂）（μ-CO）（12），获得。一个μ的形成₃ -η ³ -C ₃环在Ru ₃在180℃，这清楚地表明了这两个C的耦合于平衡的混合物的热解中观察到平面_2层放置在三钌的每个面上的部分飞机。