Amidinatogermylene Derivatives of Ruthenium Carbonyl: New Insights into the Reactivity of [Ru<sub>3</sub>(CO)<sub>12</sub>] with Two-Electron-Donor Reagents of High Basicity
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The reactivity of ruthenium carbonyl with amidinatogermylenes of the type Ge(R2bzam)tBu (R2bzam = N,N′-disubstituted benzamidinate) was studied for R = tBu (1tBu) and iPr (1iPr). The mono-, bi-, and/or trinuclear derivatives [Ru(1R)(CO)4], [Ru(1R)2(CO)3], [Ru2(1iPr)(CO)7], [Ru3(1tBu)(CO)11], [Ru3(1tBu)2(CO)10], and [Ru3(1R)3(CO)9] (R = tBu, iPr) were isolated in yields that depend upon the reactant ratio and the reaction temperature. The experimental data are consistent with the proposal that, at room temperature, the trinuclear complexes [Ru3(CO)12], [Ru3(1R)(CO)11], and [Ru3(1R)2(CO)10] form an adduct with the germylene 1R that may evolve through two different reaction pathways, (a) releasing a CO ligand (thus leading to the corresponding trinuclear CO-substituted product) and/or (b) cleaving the cluster framework (thus leading to mononuclear germylene-containing products). At 90 °C, additional processes are also possible, such as the reactions of 1R with [Ru(1R)(CO)4] or [Ru3(1R)3(CO)9], which both give [Ru(1R)2(CO)3], or the reactions of [Ru(1tBu)(CO)4] and [Ru(1iPr)(CO)4] with [Ru3(CO)12], which give [Ru3(1tBu)(CO)11] and [Ru2(1iPr)(CO)7], respectively. This wide reaction panorama helps rationalize previously reported outcomes of reactions of [Ru3(CO)12] with other reagents of high basicity, such as trialkylphosphines or N-heterocyclic carbenes, including results for which no satisfactory explanation has been hitherto provided.
本研究针对通式为Ge(R₂bzam)^tBu（其中R₂bzam=N,N'-二取代苯甲脒基（benzamidinate））的脒基锗烯（amidinatogermylenes），探究其与羰基钌（ruthenium carbonyl）的反应活性，所选取代基R分别为叔丁基（1^tBu）与异丙基（1^iPr）。所分离得到的单、双及三核衍生物包括[Ru(1^R)(CO)₄]、[Ru(1^R)₂(CO)₃]、[Ru₂(1^iPr)(CO)₇]、[Ru₃(1^tBu)(CO)₁₁]、[Ru₃(1^tBu)₂(CO)₁₀]以及[Ru₃(1^R)₃(CO)₉]（R=^tBu、^iPr），产物收率取决于反应物配比与反应温度。实验数据支持如下假说：室温条件下，三核配合物[Ru₃(CO)₁₂]、[Ru₃(1^R)(CO)₁₁]与[Ru₃(1^R)₂(CO)₁₀]可与锗烯1^R形成加合物，该加合物可通过两条不同反应路径发生转化：(a) 解离一分子CO配体，得到对应的三核CO取代产物；(b) 断裂簇骨架，得到含锗烯的单核产物。在90℃时，还可发生其他反应过程：例如1^R分别与[Ru(1^R)(CO)₄]或[Ru₃(1^R)₃(CO)₉]反应，均可生成[Ru(1^R)₂(CO)₃]；或是[Ru(1^tBu)(CO)₄]与[Ru(1^iPr)(CO)₄]分别与[Ru₃(CO)₁₂]反应，依次得到[Ru₃(1^tBu)(CO)₁₁]与[Ru₂(1^iPr)(CO)₇]。这一丰富的反应图景有助于合理化此前已报道的[Ru₃(CO)₁₂]与其他高碱性试剂（如三烷基膦（trialkylphosphines）、氮杂环卡宾（N-heterocyclic carbenes））的反应结果，包括迄今尚未得到合理解释的相关实验现象。
