复旦大学 无机化学IC16.pptVIP

4.2 Bond in coordination  compounds 配位化学 张祥麟 康衡 主编 中南工业大学出版社 1986年 配合物化学 张祥麟 主编 高等教育出版社 1991年 配位化合物的结构与性质 游效曾编著 科学出版社 1992年 无机化学 第三分册 [美] KF 巴塞尔 JC 科茨 著 潘德慧，李景舜 译 高等教育出版社 1989年 中级无机化学 项斯芬 姚光庆编著 北京大学出版社 2003年 Inorganic Chemistry [英] 2001 (First Edition) Catherine E. Housecroft and Alan G. Sharpe Inorganic Chemistry [美] 2004 (Third Edition) Gary L. Miessler and Donald A. Tarr 4.2.1 Crystal Field Theory 4.2.2 Molecular Orbital Theory 4.2.3 The Angular Overlap Model 4.2.1 Crystal Field Theory It’s modifications ligand field theory 1912 Hans Bethe Solid state physics 1950 used in T.M. complexes Pure CFT electrostatic ionic Ligand negative point charges symmetry consideration Split depends on the symmetry property of ligand environment Refer to : character table Magnitude of Δ [Ti(H2O)6] Factors affecting the  magnitude of Δ a、Oxidation state of the metal ion M n Δ [Ru(H2O)6] Δ=19800 cm [Ru(H2O)6] Δ=28600 cm b、Nature of the metal ion In a given group the trend being 3d4d5d Spectrochemical series I Br S SCN Cl N3 , F OH ox , O H2O NCS py, NH3 en bpy, phen NO2 CN CO Jφgensen For Oh (octahedron) Δo= f·g f =1, f =0.7, f =1.7 f：field strength factor g: metal ion characteristic factor 8000-36000 cm Selected values of f and g factors Problem Arrange the following ligand in order of increasing field strength: Br , F , CN , NH3 , OH , H2O P : an average pairing energy the energy necessary to cause electron pairing in a single orb ΔoP weak field high spin condition ΔoP strong field low spin complexes CFSE (LFSE) = (-0.4x+0.6y)Δo+mp For Oh field, dn n=x+y Tetrahedral sym