Sulfonated polyphenylene-sulfide(SPPS)was used as ligands in place of phosphine in Rh-complexes to yield a water-soluble catalyst for hydroformylation of higher olefins in two phasic system.The decreasing catalytic ac...Sulfonated polyphenylene-sulfide(SPPS)was used as ligands in place of phosphine in Rh-complexes to yield a water-soluble catalyst for hydroformylation of higher olefins in two phasic system.The decreasing catalytic activities and increasing n/b ratios(normal to branch aldehyde ratios)have been found respectively with increasing molar ratios of SPPS to rhodium,and with lowering of reaction temperature,indicating more or less coordinations between thioether sulfides and Rh species in SPPS-Rh compounds,The coordinations were also evidenced by a weak Reman hand observation of the SPPS-Rh compounds at 264 cm^(-1).展开更多
The X-ray crystal structures of(NH4)2(15-crown-5)3[Cu(mnt)2](1)and(NH4)2(benzo-15-crown-5)4-[Cu(mnt)2]ident to 0.5H2O(2)were determined.Two single crystals arecomposed of distinct structures of ammonium-crown ether su...The X-ray crystal structures of(NH4)2(15-crown-5)3[Cu(mnt)2](1)and(NH4)2(benzo-15-crown-5)4-[Cu(mnt)2]ident to 0.5H2O(2)were determined.Two single crystals arecomposed of distinct structures of ammonium-crown ether supramolecular cation and[Cu(mnt)2]^(2-)anion.The triple-decker dication in complex 1 and a sandwich dimmer in complex 2 wereobserved.X-Band EPR studies on the single crystals of both complex 1 and complex 2 have been carriedout at room temperature,which revealed that complex 2 showed a perfect hyperfine structure of Cuwhereas that of complex 1 could not be observed.The principal values and direction cosines of theprincipal axes of the g and A tensors were computed by a least-squares fitting procedure.The spindensity of Cu(ll)was estimated according to the principal values of the A tensors and compared wellwith the results calculated based on DFT method.展开更多
基金Work supported by the postdoctoral Foundation of National Education Commission of China the Natural Science Foundation of Fujian Province
文摘Sulfonated polyphenylene-sulfide(SPPS)was used as ligands in place of phosphine in Rh-complexes to yield a water-soluble catalyst for hydroformylation of higher olefins in two phasic system.The decreasing catalytic activities and increasing n/b ratios(normal to branch aldehyde ratios)have been found respectively with increasing molar ratios of SPPS to rhodium,and with lowering of reaction temperature,indicating more or less coordinations between thioether sulfides and Rh species in SPPS-Rh compounds,The coordinations were also evidenced by a weak Reman hand observation of the SPPS-Rh compounds at 264 cm^(-1).
基金Supported by the National Natural Science Foundation of China(Grant No.20490218)
文摘The X-ray crystal structures of(NH4)2(15-crown-5)3[Cu(mnt)2](1)and(NH4)2(benzo-15-crown-5)4-[Cu(mnt)2]ident to 0.5H2O(2)were determined.Two single crystals arecomposed of distinct structures of ammonium-crown ether supramolecular cation and[Cu(mnt)2]^(2-)anion.The triple-decker dication in complex 1 and a sandwich dimmer in complex 2 wereobserved.X-Band EPR studies on the single crystals of both complex 1 and complex 2 have been carriedout at room temperature,which revealed that complex 2 showed a perfect hyperfine structure of Cuwhereas that of complex 1 could not be observed.The principal values and direction cosines of theprincipal axes of the g and A tensors were computed by a least-squares fitting procedure.The spindensity of Cu(ll)was estimated according to the principal values of the A tensors and compared wellwith the results calculated based on DFT method.
