北京大学中级无机化学

什么是无机化学？InorganicChemistryisanyphaseofInorganicChemistryisanyphaseofInorganicChemistryisanyphaseofInorganicChemistryisanyphaseofchemistryofinteresttoaninorganicchemistchemistryofinteresttoaninorganicchemistchemistryofinteresttoaninorganicchemistchemistryofinteresttoaninorganicchemist应用和理论1.1.1.1.应用研究：配位化学为基础生命化学::::金属离子在生命中的作用材料化学::::分子基材料一、无机化学学科的现状和发展对CCCC60606060进行化学修饰，生成与OsOsOsOs的配合物：[Os(O)[Os(O)[Os(O)[Os(O)[Os(O)[Os(O)[Os(O)[Os(O)44444444(py)(py)(py)(py)(py)(py)(py)(py)22222222(C(C(C(C(C(C(C(C6666666600000000)])])])])])])])]91919191年，BerkeleyBerkeleyBerkeleyBerkeley的HawkinsHawkinsHawkinsHawkins用此化合物得到CCCC60606060的XXXX射线照片血红蛋白的血红素中心肌红蛋白的结构,Fe,Fe,Fe,Fe被多肽链包围WOWOWOWO3-x3-x3-x3-x晶体剪切面的高分辩电镜图，研究固体的缺陷CuCuCuCu原子在SiSiSiSi表面的STMSTMSTMSTM照片（放大250million)250million)250million)250million)KKKK2222Pt(CN)Pt(CN)Pt(CN)Pt(CN)4444.0.3Br.3H.0.3Br.3H.0.3Br.3H.0.3Br.3H2222OOOO配合物((((分子导线))))2222....基础研究::::量子化学为基础,,,,波谱学方法新型无机化合物的合成,,,,反应机理,,,,结构表征近3000300030003000万种（CACACACA登录到2000200020002000年）、20202020世纪末，每年报导100100100100万种，美国的化学物质的产值为4000400040004000亿美元红外光谱分析金属有机化合物的结构分子轨道理论分析FeCpFeCpFeCpFeCp2222化学键1.1.1.1.普通无机化学::::元素周期表为基础((((一年级))))2.2.2.2.无机化学((((三年级),),),),主干基础课((((中级无机化学,,,,现代无机化学,,,,无机化学新兴领域等))))二、课程的安排和要求教材::::讲义++++参考书++++文献要求:1.:1.:1.:1.课堂讲授,,,,掌握基本概念和基本内容2.2.2.2.参考书和文献阅读((((中英文))))教学环节安排((((除课堂讲授外):):):):习题(5-10(5-10(5-10(5-10分))))抽查,,,,用A4A4A4A4纸做课堂练习(5-10(5-10(5-10(5-10分))))期中考(20(20(20(20分))))期末考(60-65(60-65(60-65(60-65分))))答疑::::每周一次北大主页→→→→化学学院→→→→教师FTPFTPFTPFTP→→→→无机化学→→→→姚光庆化学楼S-303S-303S-303S-303Email:[e-mail]:[e-mail]:[e-mail]:[e-mail]扬展澜老师（化学楼S-438S-438S-438S-438）第一章酸碱化学1.1.1.1.元素在周期表中的酸碱性2.2.2.2.酸碱质子理论和酸碱概念的相对性3.Lewis3.Lewis3.Lewis3.Lewis酸碱4.4.4.4.软硬酸碱元素周期表中酸性和碱性元素的分布区域1.1.1.1.元素在周期表中的酸碱性第一过渡系金属的氧化态和酸性的关系2.酸碱概念的相对性醋酸为碱：CH3COOH+H2SO4⎯→CH3COOH2++HSO4−醋酸为酸：CH3COOH+H2O⎯→H3O++CH3COO−H2SO4为碱：H2SO4+HClO4⎯→H3SO4++ClO4−H2SO4为酸：H2SO4+HNO3⎯→H2NO3++HSO4−（硝化反应）溶剂的拉平效应（levelingeffectlevelingeffectlevelingeffectlevelingeffect）HI+H2O⎯→⎯→⎯→⎯→H3O＋＋I−−−−HBr+H2O⎯→⎯→⎯→⎯→H3O＋＋Br−−−−HI和HBr均被拉平为H3O＋，在水溶液中不能区分HIHIHIHI和HBrHBrHBrHBr的强弱NHNHNHNH2222−−−−+H+H+H+H2222OOOO⎯→⎯→⎯→⎯→NHNHNHNH3333＋OHOHOHOH−−−−CHCHCHCH3333−−−−+H+H+H+H2222OOOO⎯→⎯→⎯→⎯→CHCHCHCH4444＋OHOHOHOH−−−−在水溶液中不能区分NHNHNHNH2222−−−−和CHCHCHCH3333−−−−的强弱水中KKKKaaaa1111的酸，都被水拉平；而pKpKpKpKaaaa14141414的共轭碱也被水拉平pKpKpKpKaaaa在0000到14141414不能被拉平之间水的分辨宽度为14141414液氨中2222NHNHNHNH3333⎯⎯⎯⎯⎯⎯⎯⎯NHNHNHNH−−−−2222+NH+NH+NH+NH4444++++pKpKpKpK=33=33=33=33液氨的分辨宽度为33333333常用溶剂的分辨宽度3.3.3.3.LewisLewisLewisLewis酸碱((((电子酸碱))))A+:BA+:BA+:BA+:B⎯→⎯→⎯→⎯→A:BA:BA:BA:B酸碱酸碱加合物AsCH3CH3CH3AAAAllllAAAAllllClClClClClClClClClClClClClClClClClClClClClClClClAlAlAlAlClClClClClClClClClClClClBClBClBClBCl3333,BF,BF,BF,BF3333PPhPPhPPhPPh3333,NH,NH,NH,NH3,3,3,3,RORORORO2222,RS,RS,RS,RS2222酸碱LewisLewisLewisLewis酸碱的分子轨道示意图AlClAlClAlClAlCl3333(Lewis(Lewis(Lewis(Lewis酸))))作为傅氏烷基化反应的催化剂((((HardHardHardHardandSoftAcidsandBasesandSoftAcidsandBasesandSoftAcidsandBasesandSoftAcidsandBases，HSABHSABHSABHSAB）用于LewisLewisLewisLewis酸碱和BrBrBrBrøøøønstednstednstednsted酸碱对AlAlAlAl3+3+3+3+的配位能力FFFF−−−−ClClClCl−−−−BrBrBrBr−−−−IIII−−−−对HgHgHgHg2+2+2+2+的配位能力FFFF−−−−ClClClCl−−−−BrBrBrBr−−−−IIII−−−−亲石元素：CaCaCaCaCOCOCOCO3333,,,,LiLiLiLi2222COCOCOCO3333,,,,CaCaCaCaFFFF2222,,,,TiTiTiTiOOOO2222,,,,ZrZrZrZrOOOO2222,,,,亲硫元素::::AsAsAsAs2222SSSS3333,,,,HgHgHgHgS,S,S,S,CuCuCuCu2222S,S,S,S,Cd,Zn,Co,Fe,Sb,BiCd,Zn,Co,Fe,Sb,BiCd,Zn,Co,Fe,Sb,BiCd,Zn,Co,Fe,Sb,Bi4.4.4.4.软硬酸碱原理AcidsAcidsAcidsAcids:Cu:Cu:Cu:Cu++++,Ag,Ag,Ag,Ag++++,,,,AuAuAuAu++++,Tl,Tl,Tl,Tl++++,Hg,Hg,Hg,Hg+,2++,2++,2++,2+,,,,PdPdPdPd2+2+2+2+,Pt,Pt,Pt,Pt2+2+2+2+,Cd,Cd,Cd,Cd2+2+2+2+,,,,(BH(BH(BH(BH3333),),),),MMMM0000BasesBasesBasesBases:H:H:H:H––––,,,,RRRR––––,,,,CCCCNNNN––––,,,,IIII––––,,,,CCCCOOOO,,,,SSSSCNCNCNCN––––,R,R,R,R3333P,CP,CP,CP,C6666HHHH6666,,,,RRRR2222S,S,S,S,AcidsAcidsAcidsAcids:Fe:Fe:Fe:Fe2+2+2+2+,Co,Co,Co,Co2+2+2+2+,,,,NiNiNiNi2+2+2+2+,Cu,Cu,Cu,Cu2+2+2+2+ZnZnZnZn2+2+2+2+,,,,PbPbPbPb2+2+2+2+,SO,SO,SO,SO2222,BBr,BBr,BBr,BBr3333BasesBasesBasesBases::::NNNNOOOO2222––––,,,,SOSOSOSO33332222––––,,,,BrBrBrBr––––,,,,NNNN3333––––,,,,NNNN2222,C,C,C,C6666HHHH5555N,N,N,N,SCSCSCSCNNNN––––,,,,AcidsAcidsAcidsAcids:H:H:H:H++++,Li,Li,Li,Li++++,,,,NaNaNaNa++++,,,,KKKK++++,Be,Be,Be,Be2+2+2+2+,Mg,Mg,Mg,Mg2+2+2+2+,,,,CaCaCaCa2+2+2+2+,Cr,Cr,Cr,Cr2+2+2+2+,Cr,Cr,Cr,Cr3+3+3+3+,,,,AlAlAlAl3+3+3+3+,SO,SO,SO,SO3333,BF,BF,BF,BF3333BasesBasesBasesBases:F:F:F:F––––,,,,OHOHOHOH––––,,,,HHHH2222O,O,O,O,NHNHNHNH3333,,,,COCOCOCO33332222––––,,,,NONONONO3333––––,,,,OOOO2222––––,,,,SOSOSOSO44442222––––,,,,POPOPOPO44443333––––,,,,ClOClOClOClO4444––––SoftSoftSoftSoftBorderlineBorderlineBorderlineBorderlineHardHardHardHardPtPtPtPtIrIrIrIrTlTlTlTlCuCuCuCuAgAgAgAgAuAuAuAuPdPdPdPdCdCdCdCdHgHgHgHg典型的软酸三角形硬酸：碱金属，碱土金属，轻和高价的金属离子软酸：重过渡金属离子，低价或零价金属硬碱：半径小，不易被极化软碱：半径大，易被极化Cu(I),Cu(II)Cu(I),Cu(II)Cu(I),Cu(II)Cu(I),Cu(II)，氧化态增高，硬度加大Fe(II),Fe(III),Fe(VI)Fe(II),Fe(III),Fe(VI)Fe(II),Fe(III),Fe(VI)Fe(II),Fe(III),Fe(VI)KKKK2222FeOFeOFeOFeO4