水溶性铑膦配合物HRh(CO)(TPPTS)_3及其相关体系的--1H-NMR研究

在液体高分辨nMr谱仪上， 测定并比较了具有高效烯烃氢甲酰化活性的水溶性铑膦配合物HrH（CO）（TPPTS）3 及与此有关的配体TPPTS和OTPPTS分别在d2O、混合溶剂d2O-THf（d8）-Cd3Od中的1H-nMr谱图， 并借助1H-1H COSy谱对上述3 种化合物的1H-nMr谱峰进行了指认； 讨论了影响化学位移和偶合常数的因素， 为水溶性铑膦配合物催化剂的结构与催化性能的关联及新催化剂设计研究提供了基础数据.国家自然科学基金;教育部优秀年轻教师基

关于“经济发展方式转变进程中的财税政策”的探讨(笔谈)

转变经济发展方式是当前中国的热门话题,而上海在城市发展中又肩负着率先转变的重要任务,在这一意义和背景下,2010年4月24日由上海金融学院学院主办、上海金融学院公共经济管理学院承办的“《中国城市财政发展报告2009/2010:促进‘两个中心’建设的上海城市财政》首发式暨‘经济发展方式转变进程中的财税政策’论坛“在我校举行。与会专家围绕经济发展方式转变进程中的财税政策的“趋势与目标“、“机遇和挑战“、“实施方略“和“地方实践“等四个专题进行研讨,各抒己见,智慧交锋。现将其真知灼见整理摘要与读者分享,以期待更多学者共同关注当前经济发展方式转变进程中的财税政策

NMR Characterization and Catalytic Hydroform ylation of Water-Soluble Rhodium -Phosphine Com plex in the Presence of Acid and Base

联系人: 袁友珠. 第一作者: 张　宇, 男, 27 岁, 博士.[中文摘要]31P(1H)NMR和1H NMR 研究表明, 当NaOH 加入到水溶性铑膦配合物HRh(CO)·(TPPTS)3 [TPPT S:P(m-C6H4SO3Na)3] 后,可观察到有少量的OTPPTS[OTPPTS: O= P( m-C6H4SO3Na)3]出现,但配合物的特征谱峰即使在高浓度的NaOH 存在下也基本保持不变,表明 NaOH对配合物分子结构的影响较小;当吡啶加入到HRh(CO)(TPPTS)3中,31P(1H)NMR谱图中出现游离配体TPPTS 的31P谱峰及若干结构未知的新水溶性配合物的31P谱峰, 表明吡啶分子将与配合物分子中的配体T PPTS 发生配体交换反应.在HRh(CO)(TPPTS)3 中分别加入一定量的HCl,HNO3,H2SO4和H3PO4等无机酸时,随着酸量的增加,配合物的31P物种含量逐渐下 降,而OTPPTS 量明显上升,直至配合物31P物种完全消失; 高浓度乙酸对配合物结构的影响与 上述无机酸类似.HRh(CO)(TPPTS)3的1-己烯氢甲酰化催化反应结果表明, 碱存在下可获得较高的正异构醛比值, 但催化活性降低; 酸存在下所得产物正异构醛比值相对较低且呈淡黄色. 可见,酸对HRh(CO)(TPPTS)3的结构和性能的影响比碱大.国家自然科学基金;中国石油化学总公司联合资助“九五”重大项

NMR Characterization and Catalytic Hydroform ylation of Water-Soluble Rhodium -Phosphine Com plex in the Presence of Acid and Base

[中文文摘]31P(1H)NMR和1H NMR 研究表明, 当NaOH 加入到水溶性铑膦配合物HRh(CO)·(TPPTS)3[TPPTS: P(m-C6H4SO3Na)3]后,可观察到有少量的OTPPTS[OTPPTS:O=P(m-C6H4SO3Na)3]出现,但配合物的特征谱峰即使在高浓度的NaOH 存在下也基本保持不变,表明 NaOH 对配合物分子结构的影响较小;当吡啶加入到HRh (CO)(TPPTS)3中,31P(1H)NMR 谱图中出现游离配体TPPT S 的31P谱峰及若干结构未知的新水溶性配合物的31P谱峰, 表明吡啶分子将与配合物分子中的配体TPPTS 发生配体交换反应.在HRh(CO)(TPPTS)3中分别加入一定 量的HCl,HNO3,H2SO4和H3PO4等无机酸时,随着酸量的增加, 配合物的31P物种含量逐渐下降,而OT PPTS 量明显上升, 直至配合物31P物种完全消失; 高浓度乙酸对配合物结构的影响与上述无机酸类似.HRh(CO)(TPPTS)3的1-己烯氢甲酰化催化反应结果表明, 碱存在下可获得较高的正异构醛比值, 但催化活性降低; 酸存在下所得产物正异构醛比值相对较低且呈淡黄色.可见,酸对HRh(CO)(TPPTS)3的结构和性能的影响比碱大.国家自然科学基金;中国石油化学总公司联合资助“九五”重大项

Influence of Metal Salt on Molecular Structure of Watersoluble Rhdiumphosphine Complex

联系人及第一作者: 袁友珠, 男, 36 岁, 博士, 教授.[中文文摘]用高分辨ＮＭＲ研究了ＮａＣｌ、ＮｉＳＯ４、ＣｕＳＯ４、Ｆｅ２（ＳＯ４）３和Ｃｒ２（ＳＯ４）３对水溶性铑膦配合物ＨＲｈ（ＣＯ）（ＴＰＰＴＳ）３［ＴＰＰＴＳ：Ｐ（ｍ－Ｃ６Ｈ４ＳＯ３Ｎａ）３］分子结构的影响．３１Ｐ（１Ｈ）和１ＨＮＭＲ谱显示，于室温下在ＨＲｈ（ＣＯ）（ＴＰＰＴＳ）３中加入的ＮａＣｌ或ＮｉＳＯ４对配合物的特征３１Ｐ（１Ｈ）和１ＨＮＭＲ谱峰无明显影响；当加入ＣｕＳＯ４后，配合物的Ｒｈ—Ｈ质子峰强度弱化明显，进而消失，且原配合物的特征磷谱峰强度减弱，新生成的磷物种谱峰逐渐成为磷谱的主要物种．当加入Ｆｅ２（ＳＯ４）３或Ｃｒ２（ＳＯ４）３后，三价金属离子的强顺磁性使ＮＭＲ灵敏度下降，谱峰宽化，该２种盐均易与水溶性铑膦配合物产生强烈的相互作用，易使配合物特征谱峰消失．实验结果表明，上述金属盐对配合物结构破坏性大小的顺序为：Ｆｅ２（ＳＯ４）３＞Ｃｒ２（ＳＯ４）３＞ＣｕＳＯ４ＮｉＳＯ４～ＮａＣｌ[英文文摘]The molecular structure of water-soluble phosphine-rhdium complex HRh( CO) ·( TPPTS)3[TPPTS:P(m-C6H4SO3Na)3] affected by the metal salts, e.g.,NaCl,NiSO4,CuSO4,Fe2(SO4)3 and Cr2(SO4)3 was investigated in connection with the biphasic catalysis system by means of high resolution liquid NMR. No evident change in the spectra of 31P(1H) NMR and 1H NMR of the water-soluble complex was observed by addition of NaCl and NiSO4. When CuSO4 was added into the complex, however,the peak intensity of 1H NMR due to H—Rh diminished and accompanied with the gradual disappear ance of the phosphor us species of the complex and the appearance of the new -born phosphorus species in the 31P(1H) NMR spectra. Moreover,the characteristic twin signals of the complex at D=44.8,43.6 in the 31 P( 1H) NMR w ere completely replaced by the new complexes at D=28.0—33.4 when Fe2(SO4)3 was added. The similar result was obtained in the case of Cr2(SO4)3,when higher concent ration of Cr2(SO3)4 was used. The resul ts obtained shown that a decreasing order of influence of salt on the molecular structure of the complex is: Fe2(SO4)3> Cr2(SO3)4>CuSO4m NiSO4～NaCl.国家自然科学基金,中国石油化学工业总公司联合资助“九五”重大项目资

NMR characterization and catalytic hydroformylation of water-soluble rhodium-phosphine complex in the presence of acid and base

When NaOH was added into D2O-soiution of HRh(CO) (TPPTS)(3)[TPPTS: P(m-C6H4SO3Na)(3), trisodium salt of tri-(m-sulfophenyl)-phosphine], there were no changes in the characteristic peaks for the water-soluble complex although a small peak at delta 35.1 for OTPPTS[OTPPTS: O = P(m-C6H4SO3Na)(3), trisodium salt of tri-(nz-sulfophenyl)-phosphine oxide] was formed under a high concentration of NaOH, as evidenced by the spectra of P-31(H-1) NMR and H-1 NMR, indicating that the influence on the molecular structure of the complex by NaOH may be limited. Several new signals at delta 29-34 accompanied by the appearance of free ligand TPPTS at delta - 5.0- - 5.3 appeared in the P-31(IH) NMR spectra when pyridine was introduced into HRh(CO)(TPPTS)(3), probably due to the reaction of ligand exchange among the coordinated ligands(such as TPPTS, hydrogen, and CO) in the complex HRh(CO) (TPPTS)(3) and pyridine molecule. The water-soluble complex can be readily decomposed, however, when inorganic acids such as HCl, H2SO4, HNO3 and H3PO4 were introduced into the D2O-solution of HRh(CO)(TPPTS)(3), as shown in P-31(H-1) NMR spectroscopic data. The decomposition of the complex was completed by the formation of OTPPTS at delta 35. 1 and some new phosphate species at delta 27-29 in the P-31(H-1) NMR spectra in the presence of above inorganic acids. Analogous results to those by addition of inorganic acid were obtained when acetate acid was exceeded in mole ratio to HRh(CO)(TPPTS)(3). An increment in n/i ratio of heptyl aldehydes and a depression in TOF were obtained in case of the addition of base, in contrary, a lower n/i ratio of aldehydes in yellowish product was obtained in case of the addition of acid in I-hexene hydroformylation catalyzed by HRh (CO)(TPPTS)(3). The results obtained showed that the molecular structure and catalytic performance of HRh (CO)(TPPTS)(3) may be affected by acid more disserviceably than by base

Influence of metal salt on molecular structure of water-soluble rhdium-phosphine complex

The molecular structure of water-soluble phosphine-rhdium complex HRh(CO) . (TPPTS)(3) [TPPTS: P(m-C6H4SO3Na)(3)] affected by the metal salts, e.g., NaCl, NiSO4, CuSO4, Fe-2(SO4)(3) and Cr-2(SO4)(3) was investigated in connection with the biphasic catalysis system by means of high resolution liquid NMR. No evident change in the spectra of P-31(H-1) NMR and H-1 NMR of the water-soluble complex was observed by addition of NaCl and NiSO4. When CuSO4 was added into the complex, however, the peak intensity of H-1 NMR due to H-Rh diminished and accompanied with the gradual disappearance of the phosphorus species of the complex and the appearance of the new-born phosphorus species in the P-31(H-1) NMR spectra. More over, the characteristic twin signals of the complex at delta=44.8, 43.6 in the P-31(H-1) NMR were completely replaced by the new complexes at delta = 28.0-33.4 when Fe-2(SO4)(3) was added. The similar result was obtained in the case of Cr-2(SO4)(3), when higher concentration of Cr-2(SO3)(4) was used. The results obtained shown that a decreasing order of influence of salt on the molecular structure of the complex is: Fe-2(SO4)(3)>Cr-2 (SO3)(4)>CuSO4>>NiSO(4)similar to NaCl