镍、钴、钯、铁2-(二苯基膦基)吡啶配合物的合成及其催化羰基化反应  

The Synthesis of Complexes of 2-(Diphenylphosphino)pyridine with Nickle, Cobalt, Palladium, Iron and Their Catalytic Activity for the Carbonylation of Ethanol to Ethyl Propionate

作　　者：关新新[1] 赵维君[1] 张书笈[1] 方延铨[1] 云希勤[1] 寇登民[1] 李艳红[1] 

机构地区：[1]南开大学化学系,天津300071

出　　处：《分子催化》1992年第4期303-307,共5页Journal of Molecular Catalysis(China)

摘　　要：众所周知,铑催化剂是醇类羰基化的有效催化剂,但是铑价格昂贵且对设备有腐蚀性,因此,寻找出对醇类羰基化催化活性好的非贵金属催化剂,对醇类羰化的工业化有十分重要的意义。 本文在温和条件下,合成了四种含有相同配体（Ph₂PPy）不同金属的有机配合物（金属基分别为Ni、Co、Pd、Fe）,并探索了它们对乙醇羰基化反应的催化活性。It is well known that rhodium is the best catalyst for the carbonylation of alcohols. Rh is a noble metal, so it is desirable to find some non-noble metal catalysts to take its place. In this paper four organometallic complexes of Ⅷ group metals were synthesized under mild conditions. The crystalline parameters and molecular structures for two of the four complexes were obtained by X-ray diffraction analysis. They are (Ph2PPy)2PdCl20. 5CH2Cl2:a(A) = 8. 050(1), b (A)= 20.152(4), c(A) = 23. 067(9), R = 0. 059, Rw=0. 071, Z=4; and (Ph2PPy)2Ni(CO)2: a(A)= 12. 044(3), b(A) = 21. 322(5), c(A) = 24. 925(5), R=0. 051, Rw=0. 055, Z=8. They may be good intermediates for synthesizing binuclear organometallic complexes, because each of them has two ligands with two uncoordinated nitrogen atoms. The catalytic activity of these four complexes for the carbonylation of ethanol were tested. The best experimental condition has been found to be. temperature 423 K, CO pressure 2. 5 Pa. The catalytic activity follows the order- (Ph2PPy)2Ni (CO)2 > (Ph2PPy)2PdCl2 ?0. 5CH2C12 > (Ph2PPy)2CoCl2 > (Ph2PPy)2Fe(CO)2(CS2). (Ph2PPy)2Ni(CO)2is the best catalyst with conversion of ethanol 94. 8% and selectivity to ethyl propionate 93. 3%. As for (Ph2PPy)2Fe(CO)2(CS2), little ethyl propionate is obtained. This is in accord with Falbe's conclusion. It is often reported that the carbonylation of alcohols is carried out under high CO pressure, but the CO pressure used in this work is only 2. 5 MPa.

关 键 词：膦 配体 络合物 羰化反应 镍 钴 

分 类 号：O614.813[理学—无机化学]