水溶性铑－膦配合物的结构及性能表征

Characterization and Catalytic Properties of Water-Soluble Rhodium Complexes in Olefine Hydroformylation

采用ＩＣＰ、ＦＴＩＲ、１３ＣＷＲ、３１ＰＮＭＲ、ＴＧＡ、ＸＰＳ等方法，对三种水溶性铑配合物：ＨＲｈ（ＣＯ）（ＴＰＰＴＳ）３、ＲｈＣｌ（ＣＯ）（ＴＰＰＴＳ）２和ＲｈＩ（ＣＯ）（ＴＰＰＴＳ）２的组成、结构和性质进行了表征．结果表明，采用新设计的方法合成的水溶性铑－膦配合物，具有以三苯基膦为配体的配合物类似的结构．它们的热稳定性很好，在水中的溶解度大，而在非极性有机溶剂中极难溶解，是良好的烯烃氢甲酰化催化剂．

TPPTS(P(m-C6H4SO3Na)3) and three water soluble rhodium complexes,RhCl(CO)(TPPTS)2,HRh(CO)(TPPTS)3,and.RhCl(TPPTS)3 were prepared by a modified method with high yield (90%).RhI(CO)(TPPTS)2 was synthesized from RhCl(CO)(TPPTS)2 via ion exchange(yield:85%).The elemental composition of the compounds determined by ICP are in agreement with the proposed formula, The structure of TPPTS and rhodium complexes are characterized by FTIR and 31PNMR.13CNMR of TPPTS exhibited C1:δ=137.4 ppm,Jp-c=11.9 Hz; C2:δ=137.3 ppm,Jp-c=19. 6 Hz;C3:δ=144.1 ppm,Jp-c=6.5 Hz;C4:δ=127. 5 ppm,Jp-c=0 Hz;C5:δ=130.5ppm,Jp-c=8. 3 Hz;C6:δ=131.1 ppm,Jp-c=20.0 Hz.XPS data suggested that electron was transfered from phosphorous of TPPTS to rhodium and binding energy 3d5/2 of rhodium in HRh(CO)(TPPTS) 3 was the lowest owing to the coordination of three molecules of TPPTS.TGA data indicated that rhodium complexes were stable up to 480℃.The catalytic activities and selectivities of four rhodium complexes in l-hexene hydroformylation were studied in biphasic catalytic svstem. The reactions were carried out in an autoclave of 100 ml under the conditions:100℃,1.0 MPa(CO/H2=1),TPPTS/Rh=16 and CTAB=0.3%.The results showed that the rhodium complexes exhibited very high activities,The TOF was about 40 mol/mol Rh·min and n/i ratio of aldehyde was over 4/1.Therefore the four rhodium complexes could easily be transformed to similar catalytic active species and were suitable catalyst precursors.