- 作者: 陳竹亭 ; 劉昭吟
- 作者服務機構: 台灣大學化學系
- 中文摘要: The benzoylformyl Pd(II) complex, Pd(PPh/sub 3/)/sub 2/( Cl)(COCOPh), thermally decomposes to the corresponding benzoyl complex by the loss of CO. The predominant route of decarbonylation is led by a reversible dissociation of a phosphine ligand. The disappearance of the benzoylformyl complex in solutions follows first order kinetics not only in the existence of excess PPh/sub 3/ but also in the absence of added PPh/sub 3/. Through the treatments of both preequilibrium and the steady state approximations to the kinetic data, the rate constants of the intramolecular acyl migration, k/sub 1/ and k/sub 2/; as well as the equilibrium constant and the individual rate constants of the reversible phosphine dissociation step, K, k/sub d/ and k /sub -d/, were determined in CHCl/sub 3/. The activation parameters for k/ sub d/, being .DELTA.H/sup .dbldag./ = 25.4 Kcal Mol/sup -1/,.DELTA.S/sup .dbldag./ = 15.9 eu, .DELTA.G/sup .dbldag./ = 20.7 Kcal Mol/sup -1/; and for k/sub -d/, being .DELTA .H/sup.dbldag./ = 13.0 Kcal Mol/sup -1/, .DELTA.S/sup .dbldag./ = - 7.9 eu, .DELTA.G/sup .dbldag./ = 15.4 Kcal Mol/sup -1/, were evaluated.
- 英文摘要: --
- 中文關鍵字: Decarbonylation; .Alpha.-Ketoacyl Complex; Kinetics; Mechanism
- 英文關鍵字: 脫羰反應;.alpha.-酮醯錯化合物;動力學;反應機構