[(NH3)4C Co(NH3),C1- and CI(NH3),CoCo(NH3)C1]+ 5. Polymerization isomerism (1) Strictly speaking, polymerization isomerism, in which n varies in the complex [MLm ]n is not isomerism. It is included in this list because it represents on additional way in which an empirical formula may give incomplete information about the nature of a complex (2)For example, all members of the following series are polymerization isomers [ Co(NH3)3(NO,)31 [Co(NH3)6ICo(NO2)61 [CO(NH3)4(NO2)2I[Co(NH3)2(NO2)4] n=2 [CO(NH,)(NO, )I[Co(NH3)2(NO2 )4]2 n=3 [ Co(NH3)6[Co(NH3)2(NO,)413 O(NH3)5 (NO2 )13I Co(NO,612 三、立体异构现象( Stereo isomerism) 1.几何异构现象( Geometrical isomerism) (1)配合物的配位数与几何构型的关系( The relationship between coordination number of mplexes and geometrical structure.) a.两配位:直线型( linear)Ag(NH3)、CuCl2 b.三配位:平面三角型 (triangle)[Hgl3 c.四配位:平面四方( square planar)PC4;正四面体 ( tetrahedron)mn(CN)2 d.五配位:三角双锥( trigonal bipyramid)[ CO(NCCH3)3]、[ Cu(dipy)2 四方锥( square pyramid)[ O(acac 六配位:正八面体( octahedron)SF6、PCl 三棱柱( trigonal prism)[Re(S2C2ph2)3 f.七配位:五角双锥( pentagonal bipyramid)Na3[ZrF] 带帽三棱柱( the one-face centred trigonal prism)(NH4)【zrF,] 带帽八面体( the one- face centred octahedron) g.八配位:立方体(cube)C8H3(立方烷) 四方反棱柱( square anti prism)[Zr(acac)] 十二面体( dodecahedron) Zr(ox) 我们将讨论四、五、六配位配合物的几何异构现象 (2)决定配合物几何异构体数目的因素: a.空间构型:例如正四面体几何构型不存在几何异构体。这是因为正四面体的四 个顶点是等价的。空间构型中等价点越多,几何异构体越少。 b.配体种类:在配合物中配体种类越多,几何异构体越多。例如,八面体配合 物:Ma(一种), Mabcdef(15种)(a、b、c、d、e、f为单齿配体)227 e.g. and 5．Polymerization isomerism (1) Strictly speaking, polymerization isomerism, in which n varies in the complex [MLm]n is not isomerism. It is included in this list because it represents on additional way in which an empirical formula may give incomplete information about the nature of a complex. (2) For example, all members of the following series are polymerization isomers: [Co(NH ) (NO ) ] 3 3 2 3 n = 1 [Co(NH ) ][Co(NO ) ] 3 6 2 6 n = 2 [Co(NH ) (NO ) ][Co(NH ) (NO ) ] 3 4 2 2 3 2 2 4 n = 2 3 5 2 3 2 2 4 2 [Co(NH ) (NO )][Co(NH ) (NO ) ] n = 3 3 6 3 2 2 4 3 [Co(NH ) ][Co(NH ) (NO ) ] n = 4 3 5 2 3 2 6 2 [Co(NH ) (NO )] [Co(NO ) ] n = 5 三、立体异构现象 (Stereo Isomerism） 1．几何异构现象 (Geometrical isomerism） (1) 配合物的配位数与几何构型的关系 (The relationship between coordination number of complexes and geometrical structure.) a．两配位：直线型 (linear) + 3 2 Ag(NH ) 、 − CuCl 2 b．三配位：平面三角型 (triangle) − [HgI ] 3 c．四配位：平面四方 (square planar) 2− PtCl4 ; 正四面体 (tetrahedron) 2− Zn(CN)4 d．五配位：三角双锥 (trigonal bipyramid) + [Co(NCCH ) ] 3 5 、 + [Cu(dipy) I] 2 四方锥 (square pyramid) [VO(acac) ] 2 e．六配位：正八面体 (octahedron) SF6 、 − PCl6 三棱柱 (trigonal prism) [Re(S C ph ) ] 2 2 2 3 f．七配位：五角双锥 (pentagonal bipyramid) Na [ZrF ] 3 7 带帽三棱柱 (the one-face centred trigonal prism) (NH ) [ZrF ] 4 3 7 带帽八面体 (the one-face centred octahedron) g．八配位：立方体 (cube) C8H8 （立方烷） 四方反棱柱（square anti prism） [Zr(acac) ] 4 十二面体（dodecahedron） 4 4 [Zr(ox) ] − 我们将讨论四、五、六配位配合物的几何异构现象 (2) 决定配合物几何异构体数目的因素： a．空间构型：例如正四面体几何构型不存在几何异构体。这是因为正四面体的四 个顶点是等价的。空间构型中等价点越多，几何异构体越少。 b．配体种类：在配合物中配体种类越多，几何异构体越多。例如，八面体配合 物：Ma6（一种），Mabcdef（15 种） （a、b、c、d、e、f 为单齿配体） [ (NH3 )4Co O O Co(NH3 )2Cl2 ] 2+ H H [ Cl(NH3 )3Co O O Co(NH3 )3Cl ] 2+ H H