STUDIES ON cis-trans-ISOMERIZATION AND REACTION KINETICS OF A μ, η~2-VINYL LIGAND IN A TRIOSMIUM CLUSTER |
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作者姓名: | 刘家础 A.J.DEEMING E.BOYAR S.DONOVAN-MTUNZI |
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作者单位: | Fujian Institute of Research on the Structure of Matter,Academia Sinica,Fuzhou,Department of Chemistry,University College London,U. K.,Department of Chemistry,University College London,U. K.,Department of Chemistry,University College London,U. K. |
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基金项目: | Project supported by the National Natural Science Foundation of China. |
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摘 要: | The dihydride cluster H_2O_(s_3)(CO)_(10) reacts with ethyne to give a cis-adduct [O_(s_3)H(μ,η~2-CH=CH_2)(CO)_(10)]. The high deuterated cluster D_2O_(s_3)(CO)_(10), the reaction of D_2O_(s_3)(CO)_(10)with ethyne C_2H_2 to form the vinyl product cluster [O_(s_3)D(μ, η~2-CH=CHD)(CO)_(10)], and thereaction of H_2O_(s_3)(CO)_(10) with the deuterated ethyne C_2D_2 to form [O_(s_3)H(μ,η~2-CD=CDH)(CO)_(10)] have been reported primarily in this paper. The two cis-adducts undergo cis-trans-isomerization of μ,η~2-vinyl ligands under a small amount of the nucleophile pyridine. Usingthe combination of deuteration and dynamic ~1H,~2H NMR spectra, we report the experimen-tal evidence determined by the dynamic ~1H, ~2H NMR spectra, mechanism, and kinetic dataof the isomerization.
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