螯合型羰基铑配合物催化甲醇羰基化反应的机理研究_张抒峰.pdfVIP

2009 67 1 , 59 64 ·· ACTA CHIMICA SINICA Vol. 67, 2009 No. 1, 59 64 , , . ; *,a b b *,b (a 300387) (b 100080) [Rh(CO)2I2] , . , ;; . . . , . N CH3I , N→Rh , CH3COI , Mechanism of Methanol Carbonylation Catalyzed by Chelated Carbonyl Rhodium Complex Zhang, Shufeng*,a Qian, Qinglib Guo, Cunyueb Yuan, Guoqing*,b (a College of Chemistry and Life Science, Tianjin Normal University, Tianjin 300387) (b Laboratory of New Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080) Abstract The mechanism of methanol carbonylation catalyzed by a chelated square planar carbonyl rhodium complex was studied. The chelated square planar cationic complex was formed via the coordination of [Rh(CO)2Cl]2 with the ligand, which has two donors with different coordination capacity. Experimental results showed that the active species of the catalyst in methanol carbonylation differed from [Rh(CO)2I2] reported in other literature. Other than conventional concept, the N→Rh bond, formed by rhodium in the complex and nitrogen at pyridine ring in the ligand, did not break in the course of the carbonylation reaction, but formed into new active species instead, i.e., the ligand and rhodium as a whole participated in the oxidative addition of CH3I and the formation of CH3COI. Via the investigation of the corresponding catalyst with polymer ligand, the mechanism was further demonstrated. The result is of significance towards the molecular design of such catalysts, and the solution to their deactivation due to precipitation in industrial application as well. Keywords rhodium complex; methanol carbonylation; reaction mechanism; active species , [Rh(CO)2I2] , . [1 3], ,, * E-mail: yuangq@iccas.ac.cn; Tel: 86-010Received August 14, 2007; revised August 1, 2008; accepted September 12, 2008. , , [Rh(CO)2I4] Rh . CO [4]. 60 , CO 3.0 MPa 0.5 MPa, . Monsanto [5,6], . , [7], [7 17]. I CO, Rh , ,. , , [8 11]. , [18 21]. : (1) Rh(I) ; (2) Rh(I); (3) , ; (4) . 2- [Rh(CO)2Cl]2 , CH3