新型有机配合物Ni(diphos)(CO)_2的合成及其对苯的光羰化反应

通过Ｎｉ（ｄｉｐｈｏｓ）Ｃｌ２在ＣＯ气氛下被Ｎａ（Ｈｇ）还原，合成了４种新型Ｎｉ（ｄｉｐｈｏｓ）（ＣＯ）２配合物，其中ｄｉｐｈｏｓ：ｄＣｙｐＰｅ，ｄＣｙｈＰｅ，Ｐｈ（ｔ－Ｂｕ）Ｐｅ，ＰＰ。这４种配合物均通过红外光谱和元素分析等方法确认。利用上述合成的新型Ｎｉ的双羰基双膦配合物在室温和常压下，成功地进行了苯的光羰化反应性能研究，反应产物苯甲醛和苯甲醇均经色－质分析鉴定确认。结果表明，光反应与Ｒｈ（ｄｉｐｈｏｓ）（ＣＯ）Ｃｌ配合物一样都具有较高的选择性。此外，对光羰化反应的机理作了探索。

新型有机配合物Rh(diphos)(CO)Cl的合成及其对苯的光羰化反应

利用［Ｒｈ（ＣＯ）２（μＣｌ）］２与ｄｉｐｈｏｓ反应，合成了３种新型Ｒｈ（ｄｉｐｈｏｓ）（ＣＯ）Ｃｌ配合物，其中ｄｉｐｈｏｓ＝ｄ（ｔＢｕ）Ｐｅ，ｄＣｙｈＰｅ，ｄＣｙｐＰｅ。这３种配合物均通过红外光谱和元素分析等方法测定确认。利用上述合成的新型Ｒｈ的羰基双膦配合物在室温和常压下，首次成功地进行了苯的光羰化反应性能的研究，反应产物苯甲醛和苯甲醇均经色质分析鉴定确认。结果表明，光反应都具有较高的选择性。同时对光羰化反应的机理作了合理的解释。

含膦配体的铂羰基配合物催化苯的光羰化反应

采用“原位反应”的方法 ,研究了配合物 Pt( PMe3) 2 ( CO) 2 和 Pt( diphos) ( CO) 2 ( diphos:1 ,2 -二 (二特丁基膦 )乙烷 ,即 d( t- Bu) Pe;1 ,2 -二 (二环己基膦 )乙烷 ,即 d Cyh Pe;1 ,2 -二 (二环戊基膦 )乙烷 ,即 d Cyp Pe;1 ,2 -二 (苯基特丁基膦 )乙烷 ,即 Ph( t- Bu) Pe)在室温和常压下对苯的光羰化反应性能 ,得到了预期的反应产物苯甲醛和苯甲醇 ,它们均经色 -质分析鉴定确认 .结果表明 ,该反应具有很高的选择性 .

羰基－膦－过渡金属有机配合物的合成及其对苯的光羰基化反应的研究

本文合成了一系列新的羰基－双膦和羰基－叔膦的Ｒｈ，Ｐｔ和Ｎｉ金属有机配合物，并在均相溶液里和室温常压下，研究了苯的光（λ＞２７５ｎｍ）羰基化反应，首次观察到非贵重过渡金属Ｎｉ的有机配合物可催化该反应，其催化活性与膦配体的空间效应和供电性有关，提出了苯的光羰基化反应的可能机理。

Effect of Calcination Temperature on Catalytic Activity and Textual Property of Cu/HMOR Catalysts in Dimethyl Ether Carbonylation Reaction

The effect of calcination temperature on the catalytic activity for the dimethyl ether （DME） carbonylation into methyl acetate （MA） was investigated over mordenite supported copper （Cu/HMOR） prepared by ion-exchange process. The results showed that the catalytic activity was obviously affected by the calcination temperature. The maximal DME conversion of 97.2% and the MA selectivity of 97.9% were obtained over the Cu/HMOR calcined at 430 ℃ under conditions of 210 ℃, 1.5 MPa, and GSHV of 4883 h^-1. The obtained Cu/HMOR catalysts were characterized by powder X-ray diffraction, N2 absorption, NH3 temperature program desorption, CO temperature program desorption, and Raman techniques. Proper calcination temperature was effective to promote copper ions migration and diffusion, and led the support HMOR to possess more acid activity sites, which exhibited the complete decomposing of copper nitrate, large surface area and optimum micropore structure, more amount of CO adsorption site and proper amount of weak acid centers.

Spacial hindrance induced recovery of over-poisoned active acid sites in pyridine-modified H-mordenite for dimethyl ether carbonylation

Zeolite catalysts,such as H-mordenite(H-MOR),are readily deactivated by coke deposition in carbonylation reactions.Pyridine modification of H-MOR can improve its stability but can lead to an undesirable loss in catalytic activity.Herein,we report the intrinsic impact of the pyridine adsorption behavior on H-MOR and the spacial hindrance of the zeolite frameworks on dimethyl ether(DME)carbonylation at a molecular level.We discovered that acid sites at O2 positions,located on common walls of eight-membered ring(8-MR)side pockets and 12-MR channels,were active in DME carbonylation,but were unfortunately poisoned during pyridine modification.Density functional theory calculations revealed that the pyridine-poisoned acid sites at the O2 positions could be easily regenerated due to the spacial hindrance of the zeolite frameworks.Accordingly,they can be facilely regenerated by proper thermal treatment,which induces 60%promotion in the catalytic activity along with a high stability.Our findings demonstrate the determining role of O2 positions in H-MOR for DME carbonylation and provide a new avenue for the rational design of other efficient zeolite-relevant catalytic systems.

Vibrational and Structural Dynamics of Mn（CO）sBr and Re（CO）sBr Examined Using Nonlinear Infrared Spectroscopy

Vibrational and structural dynamics of two transition metal carbonyl complexes, Mn（CO）5Br and Re（CO）5Br were examined in DMSO, using ultrafast infrared pump-probe spectroscopy, steady-state linear infrared spectroscopy and quantum chemistry computations. Two car- bonyl stretching vibrational modes （a low-frequency A1 mode and two high-frequency degenerate E modes） were used as vibrational probes. Central metal effect on the CO bond order and force constant was responsible for a larger E-A1 frequency separation and a generally more red-shifted E and A1 peaks in the Re complex than in the Mn complex. A generally broader spectral width for the A1 mode than the E mode is believed to be partially due to vibrational lifetime effect. Vibrational mode-dependent diagonal anharmonicity was observed in transient infrared spectra, with a generally smaller anharmonicity found for the E mode in both the Mn and Re complexes.

An efficient and facile synthesis of N-Cbz-β-aminoalkanesulfonamides

An efficient method for the synthesis of N-Cbz-β-aminoalkanesulfonamides was described.N-Cbz-β-aminoalkanesulfonamides were readily prepared in good yields from a variety of amino alcohols,including optically active ones,via N-Cbz protection with benzyl chloroformate,Mitsunobu esterification reaction with thiolacetic acid,N-chlorosuccinimide oxidation,and ammonolysis process.