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首页> 外文期刊>Indian Journal of Chemistry, Section A. Inorganic, Physical, Theoretical & Analytical >Reactions of electron-deficient benzoquinoline triosmium cluster[(mu-H)Os3(CO)9(mu 3-eta 2-C13H8N)]with diazomethane
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Reactions of electron-deficient benzoquinoline triosmium cluster[(mu-H)Os3(CO)9(mu 3-eta 2-C13H8N)]with diazomethane

机译:缺电子的苯并喹啉tri簇[(mu-H)Os3(CO)9(mu 3-eta 2-C13H8N)]与重氮甲烷的反应

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摘要

Treatment of the electron-deficient benzoquinoline triosmium cluster[(mu-H)Os3(CO)9(eta 3-eta 2-C13H8N)]1 with excess CH2N2 at 0 to 25°C leads to the formation of[(mu-H)2Os3(CO)9{mu 3-eta 2-CH(C13H8N)}]2 in 85% yield.Compound 2 is formed by insertion and subsequent C-H oxidative addition of a CH2 moiety into the ring C(8)-0s bond.Heating 2 at 98°C furnishes three new compounds[(mu-H)3Os3(CO)8(mu 3-eta 2-C(C,3H8N)}]3,[(mu-H)Os3(CO)9{mu 3-eta 2-C(Cl3H8N)}]4,and[(mu-H)2(Cl)Os3(CO)8{mu 3-eta 2-C(C13HgN))]5 in 18%,23% and 8% yields,respectively.The formation of compounds 3 and 4 involves activation of the methylidene C-H bond.Compound 5 is most probably formed from 4 via exchange of a bridging hydride with a chloride.The trihydride compound 3 reacts with CCl4 at 77°C to give the dihydrido chloro-compound 5 in 44% yield.Thermolysis of 2 in the presence of H2 at 1 atm at 80°C gives 3 in 75% yield.All the new compounds have been characterized on the basis of elemental analyses,IR,NMR and mass spectroscopic data.
机译:在0至25°C下用过量的CH2N2处理缺电子的苯并喹啉三tri簇[(mu-H)Os3(CO)9(eta 3-eta 2-C13H8N)] 1导致[[mu-H )2Os3(CO)9 {mu 3-eta 2-CH(C13H8N)}] 2的产率为85%。化合物2是通过将CH2部分插入并随后CH氧化加成到C(8)-0s环中而形成的。在98°C加热2可提供三种新化合物[(mu-H)3Os3(CO)8(mu 3-eta 2-C(C,3H8N)}] 3,[(mu-H)Os3(CO)9 {mu 3-eta 2-C(Cl3H8N)}] 4,和[(mu-H)2(Cl)Os3(CO)8 {mu 3-eta 2-C(C13HgN))] 5 in 18%,23化合物3和4的形成涉及亚甲基CH键的活化。化合物5最有可能由4通过桥联氢化物与氯化物的交换而形成。三氢化物化合物3与CCl4的反应温度为77 ℃得到二氢氯代化合物5,产率为44%。在H2存在下,在1 atm于80°C下热解2,产率为75%,产率为3%。所有新化合物均根据元素分析进行​​了表征,IR,NMR和质量光谱数据。

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