摘要
The dihydride cluster H<sub>2</sub>O<sub>s<sub>3</sub></sub>（CO）<sub>10</sub> reacts with ethyne to give a cis-adduct [O<sub>s<sub>3</sub></sub>H（μ,η<sup>2</sup>-CH=CH<sub>2</sub>）（CO）<sub>10</sub>]. The high deuterated cluster D<sub>2</sub>O<sub>s<sub>3</sub></sub>（CO）<sub>10</sub>, the reaction of D<sub>2</sub>O<sub>s<sub>3</sub></sub>（CO）<sub>10</sub>with ethyne C<sub>2</sub>H<sub>2</sub> to form the vinyl product cluster [O<sub>s<sub>3</sub></sub>D（μ, η<sup>2</sup>-CH=CHD）（CO）<sub>10</sub>], and thereaction of H<sub>2</sub>O<sub>s<sub>3</sub></sub>（CO）<sub>10</sub> with the deuterated ethyne C<sub>2</sub>D<sub>2</sub> to form [O<sub>s<sub>3</sub></sub>H（μ,η<sup>2</sup>-CD=CDH）（CO）<sub>10</sub>] have been reported primarily in this paper. The two cis-adducts undergo cis-trans-isomerization of μ,η<sup>2</sup>-vinyl ligands under a small amount of the nucleophile pyridine. Usingthe combination of deuteration and dynamic <sup>1</sup>H,<sup>2</sup>H NMR spectra, we report the experimen-tal evidence determined by the dynamic <sup>1</sup>H, <sup>2</sup>H NMR spectra, mechanism, and kinetic dataof the isomerization.
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.
基金
Project supported by the National Natural Science Foundation of China.
