A novel efficient catalyst for the hydrogenation of carbon dioxide to formic acid ruthenium bisphosphine on functionalized silica was in situ synthesized, affording turnover frequency （TOF） of 1190 h^-1 at 100% sele...A novel efficient catalyst for the hydrogenation of carbon dioxide to formic acid ruthenium bisphosphine on functionalized silica was in situ synthesized, affording turnover frequency （TOF） of 1190 h^-1 at 100% selectivity under 80℃ with total pressure of 16.0 MPa. The catalyst can be separated from the reaction mixture easily and reused with moderate loss of activity.展开更多
Complexes Cl-RuⅡ（dppe）2（Fe Cl4）·2CH2Cl2（2） and Br-RuII（dppe）2（Fe Br4）·2CH2Cl2（3） were prepared by the reaction of trans-RuII（dppe）2Cl2（1） with FeX 3（X = Cl, Br）. More interestingly, the ce...Complexes Cl-RuⅡ（dppe）2（Fe Cl4）·2CH2Cl2（2） and Br-RuII（dppe）2（Fe Br4）·2CH2Cl2（3） were prepared by the reaction of trans-RuII（dppe）2Cl2（1） with FeX 3（X = Cl, Br）. More interestingly, the central Ru atoms of RuII（dppe）-based complexes（2 and 3） define a tetragonal pyramid with five-coordination. The temperature dependence magnetic susceptibilities indicate that the xMT values of complexes 2 and 3 are almost constant at 50~300 K, and the xMT values sharply decrease with further decreasing the temperature at low temperature due to the zero-field splitting（ZFS） of high spin Fe（III） ions.展开更多
C50H46OP4ClRh, RhCl(dppm)2 · H2O, Mr = 922. 2, monoclinic, P21/2, a=10. 532(3), b=22.574(8), c=18. 641(8) A, β=93. 41(3)°, V = 4424 (3) A3, Z = 4, Dc=1. 386 g. cm-3, λ(MoKα) = 0. 71073A , F(000) = 1904. T...C50H46OP4ClRh, RhCl(dppm)2 · H2O, Mr = 922. 2, monoclinic, P21/2, a=10. 532(3), b=22.574(8), c=18. 641(8) A, β=93. 41(3)°, V = 4424 (3) A3, Z = 4, Dc=1. 386 g. cm-3, λ(MoKα) = 0. 71073A , F(000) = 1904. The structure was determined by direct methods and difference Fourier syntheses and refined by full-matrix least-squares to final R = 0. 037 and Rw = 0. 036 for 3432 (F> 6. 0σ(F) ) observed reflections. The structure of the title compound contains RhCl-(dppm)2 and non-coordinated H2O molecules. The rhodium atom is coordinated by one chlorine atom and four phosphorus atoms of two DPPM ligands forming a tetragonal pyramidal configuration.展开更多
基金the National Natural Science Foundation of China （No.20173048） the Specialized Research Fund for the Doctoral Program of Higher Education （No. 20030335068）+1 种基金 the Scientific Research Fund of Zhcjiang Provincial Education Department （No. 20040320） Zhcjiang Provincial Natural Science Foundation of China （No. Y405088）.
文摘A novel efficient catalyst for the hydrogenation of carbon dioxide to formic acid ruthenium bisphosphine on functionalized silica was in situ synthesized, affording turnover frequency （TOF） of 1190 h^-1 at 100% selectivity under 80℃ with total pressure of 16.0 MPa. The catalyst can be separated from the reaction mixture easily and reused with moderate loss of activity.
文摘Complexes Cl-RuⅡ（dppe）2（Fe Cl4）·2CH2Cl2（2） and Br-RuII（dppe）2（Fe Br4）·2CH2Cl2（3） were prepared by the reaction of trans-RuII（dppe）2Cl2（1） with FeX 3（X = Cl, Br）. More interestingly, the central Ru atoms of RuII（dppe）-based complexes（2 and 3） define a tetragonal pyramid with five-coordination. The temperature dependence magnetic susceptibilities indicate that the xMT values of complexes 2 and 3 are almost constant at 50~300 K, and the xMT values sharply decrease with further decreasing the temperature at low temperature due to the zero-field splitting（ZFS） of high spin Fe（III） ions.
文摘C50H46OP4ClRh, RhCl(dppm)2 · H2O, Mr = 922. 2, monoclinic, P21/2, a=10. 532(3), b=22.574(8), c=18. 641(8) A, β=93. 41(3)°, V = 4424 (3) A3, Z = 4, Dc=1. 386 g. cm-3, λ(MoKα) = 0. 71073A , F(000) = 1904. The structure was determined by direct methods and difference Fourier syntheses and refined by full-matrix least-squares to final R = 0. 037 and Rw = 0. 036 for 3432 (F> 6. 0σ(F) ) observed reflections. The structure of the title compound contains RhCl-(dppm)2 and non-coordinated H2O molecules. The rhodium atom is coordinated by one chlorine atom and four phosphorus atoms of two DPPM ligands forming a tetragonal pyramidal configuration.
