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Transformation of Chlorohydrocarbons and Amines in the Coordination Sphere of [(µ-H)2Os3(CO)10]
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2017-06-29 04:35:51 , DOI: 10.1002/ejic.201700411 M. Yu. Afonin 1 , B. Yu. Savkov 1 , A. V. Virovets 1 , V. S. Korenev 1 , A. V. Golovin 2 , V. A. Maksakov 1, 2
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2017-06-29 04:35:51 , DOI: 10.1002/ejic.201700411 M. Yu. Afonin 1 , B. Yu. Savkov 1 , A. V. Virovets 1 , V. S. Korenev 1 , A. V. Golovin 2 , V. A. Maksakov 1, 2
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A reaction has been found and investigated that demonstrates the potential for coordination, activation, and transformation of three organic molecules, namely, two dichloromethane molecules and one amine molecule, in the coordination sphere of the [(µ-H)Os3(CO)10]– carbonylate anion, which is formed in situ from the deprotonation of [(µ-H)2Os3(CO)10]. This reaction is very intricate and comprises such steps as the nucleophilic substitution of chloride ions by cluster carbonylate anions in the halocarbons, C–H, C–N, and C–Cl bond cleavage, and C–C and C–N bond formation under unusually mild conditions for such reactions leading to the formation of the CH=CH2- or CH=CHNR2-bearing complexes [(µ-Cl)Os3(µ2-σ,π-CH=CH2)(CO)10] and [(µ-H)Os3(µ-CH=CHNR2)(CO)10]. The reaction is sensitive to the nature of the halogen in the halocarbon. When bromine or iodine was used in place of chlorine in the halohydrocarbons, [(µ-H)Os3(µ-X)(CO)10] (X = Br, I) clusters were obtained in good yields, which apparently indicates the replacement of the SN2 mechanism by SN2Hal.
中文翻译：
[（µ-H）2Os3（CO）10]配位域中氯烃和胺的转化
已发现并研究了一种反应，该反应证明了[（µ-H）Os 3（CO）的配位领域中三个有机分子（即两个二氯甲烷分子和一个胺分子）的配位，活化和转化的潜力10 ] –羰基阴离子，它是由[（µ-H）2 Os 3（CO）10 ]的去质子化而形成的。该反应非常复杂，包括如下步骤：卤代碳中的簇状羰基化阴离子对氯离子的亲核取代，CH，CH，CN和Cl的键裂解，以及在此条件下形成CC和CN的键此类反应的异常温和条件导致CH = CH 2的形成-或带有CH = CHNR 2的配合物[（µ-Cl）Os 3（µ 2 - σ ，π-CH= CH 2）（CO）10 ]和[（µ-H）Os 3（µ-CH = CHNR 2）（CO）10 ]。该反应对卤代烃中卤素的性质敏感。当用溴或碘代替卤代烃中的氯时，可以得到高产率的[（µ-H）Os 3（µ-X）（CO）10 ]（X = Br，I）簇，这表明用S N 2Hal取代S N 2机制。
更新日期：2017-06-29
中文翻译：
[（µ-H）2Os3（CO）10]配位域中氯烃和胺的转化
已发现并研究了一种反应，该反应证明了[（µ-H）Os 3（CO）的配位领域中三个有机分子（即两个二氯甲烷分子和一个胺分子）的配位，活化和转化的潜力10 ] –羰基阴离子，它是由[（µ-H）2 Os 3（CO）10 ]的去质子化而形成的。该反应非常复杂，包括如下步骤：卤代碳中的簇状羰基化阴离子对氯离子的亲核取代，CH，CH，CN和Cl的键裂解，以及在此条件下形成CC和CN的键此类反应的异常温和条件导致CH = CH 2的形成-或带有CH = CHNR 2的配合物[（µ-Cl）Os 3（µ 2 - σ ，π-CH= CH 2）（CO）10 ]和[（µ-H）Os 3（µ-CH = CHNR 2）（CO）10 ]。该反应对卤代烃中卤素的性质敏感。当用溴或碘代替卤代烃中的氯时，可以得到高产率的[（µ-H）Os 3（µ-X）（CO）10 ]（X = Br，I）簇，这表明用S N 2Hal取代S N 2机制。
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