第一章 基本概念.pdf

配位化学Coordination Chemistry吴建中Coord_参考书目配位化学,第二版，孙为银编著,化学工业出版社,2010Geoffrey A.Lawrance.Introduction to Coordination Chemistry.Wiley,2010配位化学原理与应用，章慧等编著，化工出版社，2009Joan Ribas Gispert.Coordination Chemistry.Wiley,2008高等配位化学，朱龙观主编，华东理工大学出版社，2009配位化学(双语版)，李晖编著，化工出版社，2006配位化学,杨帆等编著,华东师范大学出版社,2009.配位化合物的结构和性质，游效曾编著，科学出版社，1992配位化学:金属配合物的化学,F.Basolo&R.C.Johnson著,宋银柱、王耕霖等译,申泮文校，北京大学出版社，1982Physical Inorganic Chemistry:A Coordination Chemistry Approach.By S.F.A.Kettle,Oxford University Press,1996配位化学(无机化学丛书第12卷),戴安邦等编著,科学出版社,1987配位化学进展,游效曾等主编,高等教育出版社,2000配位化学研究方法,金斗满、朱文祥编著,科学出版社,1996.配位化学,罗勤慧、沈孟长编著,江苏科学技术出版社,1987.稀土配位化学,黄春辉著,科学出版社,1997.配位化学的创始与现代化,孟庆金、戴安邦编,高等教育出版社,1998.配合物化学,张祥麟编著,高等教育出版社,1991.现代配位化学,徐志固编著,化学工业出版社,1987.配位化学,河南大学、南京师范大学等编,河南大学出版社,1989配位化学在工业中的应用 徐延瓞编 高等教育出版社 1989内容第一章 绪论第二章 配合物的立体化学第三章 配合物的化学键理论第四章 配合物的稳定性第五章 配位反应机理第六章 生物配合物第七章 配合物的合成第八章 配位化学研究方法第一章 绪论 Introduction1.1 配位化学的发展 Development1.2 基本概念 Basic concepts配位键 Coordinate bond中心原子 Central atom配位原子与配体 Donor atom and ligand配位数 Coordination number配位化合物 Coordination compound1.3 配位化合物命名 Nomenclature维尔纳1.1 配位化学的发展配合物在自然界中广泛存在：水合金属离子、宝石、金属蛋白、叶绿素1706年发现普鲁士蓝Fe4Fe(CN)63（兽皮或牛血与Na2CO3在铁锅中煮沸）第一个人工合成的配合物？但是直到1893年26岁的维尔纳提出配位学说，对配合物的组成和结构进行了合理解释以后，才使得配合物得到深入、系统的研究，并逐步发展出配位化学这一重要的三级学科。有系统的最早的配合物合成和结构研究CoCl3nH2O(n=3,4,5,6)Sophus Mads Jrgensen 约根森约根森(July 4,1837-April 1,1914)is considered one of the founders of coordination chemistry,and is known for the debates which he had with Alfred Werner during 1893-1899.While Jrgensens theories on coordination chemistry were ultimately proven to be incorrect,his experimental work provided much of the basis for Werners theories.Alfred Werner 维尔纳维尔纳(December 12,1866-November 15,1919)developed his theory of coordination chemistry at the age of 26,received the 1913 Nobel Prize for chemistry and in 25 years supervised 200 PhD students and published syntheses for in excess of 8000 complexes.First inorganic chemist to receive Nobel Prize.电导率，与硝酸银反应维尔纳配位理论的重要贡献维尔纳配位理论的重要贡献主价和副价主价和副价(primary and secondary valence)(primary and secondary valence)、内界和外界、内界和外界(inner and outer(inner and outer sphere)sphere)、空间构型、空间构型副价的概念补充了当时不完善的化合价理论副价的概念补充了当时不完善的化合价理论空间概念创造性地把有机化学中的结构理论扩展到无机物空间概念创造性地把有机化学中的结构理论扩展到无机物1923年 Sidgwick 提出有效原子序数(EAN)规则，揭示中心原子电子数与配位数之间的关系1930年，Pauling 提出价键理论40年代前后，分离技术和分析方法的研究发展。如萃取法、离子交换法等分离技术及分光光度法、配位滴定法等分析方法，分析分离核燃料、稀有元素和其它高纯度化合物50年代，分子轨道和晶体场理论的发展60年代以来，二茂铁、羰合物、烯烃配合物等金属有机配合物；簇合物；冠醚、穴醚配合物；生物配合物、配合物药物、配合物诊断试剂、探针；OLED、单分子磁体、非线性光学材料从诺贝尔化学奖看配位化学的发展从诺贝尔化学奖看配位化学的发展http:/nobelprize.org/nobel_prizes/chemistry/laureates/Alfred Werner配位学说开创者配位学说开创者1913Hans Fischer卟啉配合物的研究卟啉配合物的研究1930Linus Pauling价键理论等价键理论等1954Max F.Perutz 血红蛋白、肌红蛋白结构血红蛋白、肌红蛋白结构1962Karl Ziegler and Giulio Natta 配位催化配位催化1963Dorothy Crowfoot Hodgkin维生素维生素B12结构结构1964Geoffrey Wilkinsonand Ernst Otto Fischer有机金属化合物有机金属化合物1973Henry Taube 配合物反应机理配合物反应机理1983Jean-Marie Lehn,Donald J.Cram,and Charles J.Peterson超分子化学超分子化学1987Robert Huber,Joann Deisenhofer,and Hartmut Micher光合作用反应中心光合作用反应中心1988Rudolph Arthur Marcus电子转移理论电子转移理论1992K.Barry Sharpless手性催化手性催化2001Roderick MacKinnon 离子通道离子通道20031.2 基本概念基本概念Consider the complex:Central atom 中心原子中心原子 Cr(III)、CrIII、Cr3+Ligands 配体配体-molecules/ions attached to metal ion,NH3&Cl-.Donor atoms 配位原子配位原子-atoms bonded to metal ion,N on NH3&Cl-;not N,O on NO3-.Coordination number 配位数配位数-number of donor atoms?Number of coordinate bonds?6Coordinate bond 配位键配位键 Cr-N、Cr-ClCoordination entity 配位实体、配位单元？配位实体、配位单元？CrCl2(NH3)4+Counter-ion 反离子，抗衡离子反离子，抗衡离子-balances charge on complex -nitrate(NO3-)Hydrate-water present in crystal latticeCrH3NH3NNH3NH3ClClNO3H2ORe+Fe+CrCOOCNaCOML5X+LBN=6CN=2,6,11ML5X2+LBN=7CN=3,7,12ML5X-LBN=6CN=4,6,8Ligand Bond Number-LBNLBN=sum of L and X type ligands2e donors(L ligands)or 1e donors(X ligands)or 1e donors(X ligands)So,Coordination number(CN)is often ambiguous!配位化合物（配合物）定义配位化合物（配合物）定义中国化学会（1980）：配位化合物（简称配合物）是由可给出弧对电子或多个不定域电子的一定数目的离子或分子（称为配体）和具有接受孤对电子或多个不定域电子的空位的原子或离子（统称中心原子）按一定的组成和空间构型所形成的化合物。IUPAC(2004)：A coordination compound is a compound that contains a coordination entity.A coordination entity is an ion or neutral molecule that is composed of a central atom,usually that of a metal,to which is attached a surrounding array of other atoms or groups of atoms,each of which is called a ligand.其它：A coordination compound is the product of a Lewis acid-base reaction in which neutral molecules or anions(called ligands)bond to a central metal atom(or ion)by coordinate covalent bonds.A coordination compound is a chemical compound formed by joining independent molecules or ions usually to a central metallic atom by coordinate bonds.A metal complex or coordination compound is a compound formed from a Lewis acid and a Brnsted base,a Lewis acid being an electron pair acceptor and a Brnsted base a proton acceptor.文献中时见旧称“complex”，“络合物”中心原子中心原子Trends in PropertiesAtomic Size-Decreases across series Smoother steadier decrease within main group elements(outer orbitals shield increased nuclear charge poorly).Transition series-atomic size decreases then stays constant.(filled inner d-orbitals shield outer electrons(4s)from increased charge).Electronegativity and Ionization Energy Both increases across whole series but change is relatively small across transition series-small change in size!Similar to values for large main group metals(eg.,Ga,Ge).Trends within GroupsAtomic Size Increases from period 4 (3d)to 5(4d)but not from period 5(4d)to 6(5d)-offset by lanthanide contraction.Electronegativity Increases more for periods 5 and 6.High increase in nuclear charge&radius increase small.Ionization Energy(IE)-higher for period 6.Higher charge density-electrons held more tightly.Density-Highest for period 6.Large mass increases coupled with relatively little change in atomic volume.Classification of Ligands(配体分类)according to bond natures1）ligand(classical)提供孤电子对与中心原子形成 配键的配体。如：H2O,NH3,X-等-经典配合物，Werner型配合物2）acid ligand除提供孤电子对与中心原子形成配键外，还有与中心原子 d 轨道对称性匹配的空轨道(p、d 或*)，能接受中心原子提供的非键d电子对，形成反馈键的配体。如：R3P，R3As，CO，CN-等22224200(1)(2)(3)(4)(1)(5)(2)(6)3）ligand:CH2=CH2,benzene,Cp既能提供电子与中心原子形成配键，又能接受中心原子提供的非键d电子对形成反馈键的不饱和有机配体。可分为链状(烯烃、炔烃、-烯丙基等)和环状(苯、环戊二烯、环庚三烯、环辛四烯)等二类。注意：注意：配体与配体与酸配体都可形成反馈酸配体都可形成反馈键，区别在于二种配体所提供的电子来键，区别在于二种配体所提供的电子来源不同，前者提供源不同，前者提供电子，后者提供孤电子对。电子，后者提供孤电子对。Ferrocene(二茂铁)synthesized in 1951.Modern Organometallic Chemistry begins with this discoveryZeises Salt synthesized in 1827.Structure not fully known until 1975 according to donor atoms Monodentate ligand(单齿配体)Multidentate ligand(多齿配体)Bidentate Tridentate Chelating ligand(螯合配体)Bridging ligand(桥联配体)Ambidentate ligand(两可配体)Typical Monodentate LigandsF-fluoroBr-bromoI-iodoCO32-carbonatoNO3-nitratoSO32-sulfitoS2O32-thiosulfitoSO42-sulfatoCOcarbonyl 羰基羰基Cl-chloroO2-oxoO22-peroxoOH-hydroxo 羟基羟基NH2-amidoCN-cyanoSCN-thiocyanoNO2-nitroH2OaquaNH3ammineCH3NH2methylamineP(C6H5)3triphenylphosphineAs(C6H5)3Triphenyl arsineN2dinitrogenO2dioxygenNOnitrosylC2H4ethyleneC5H5NpyridineCan be bidentateCommon bridging ligands,also ambidentate.Typical multidentate ligandsNH2H2Nethane-1,2-diamine(ethylenediamine,en)NHH2NNH2NHH2NNHNH2NCOOHHOOCNethylenediaminetetraaceticacid(H4edta)COOHHOOCdientren乙二胺二乙三胺三乙四胺乙二胺四乙酸乙二胺二乙三胺三乙四胺乙二胺四乙酸2,2-邻菲咯啉1,10-菲咯啉2,2-联吡啶acetylacetonato(acac)NNN2,2:6,2”-terpyridine2,2:6,2”-三(联)吡啶NH2CH2COO-glycinato(gly)甘氨酸根同一配体可能采取不同配位方式Harris NotationJ.Chem.Soc.,Dalton Trans.,2000,23492356X.AaBbCcX 中心原子总数A、B、C.不同配位原子所连中心原子数，配位原子的先后按S、O、N轻重顺序a、b、c配位原子对应的中心原子位置，如无歧义，不需标注ChelatesMetals and Chelates in Living SystemsPorphyrinsChlorophyllHaemoglobinPorphineClassification of coordinaiton compounds According to central atom Mononuclear complex(单核配合物)Multinuclear(多核)Homonuclear(同核)Heteronuclear(异核)According to ligand polypyridine(polypyridyl)complex(多吡啶配合物)halogen complex(卤素配合物)porphyrin complex(卟啉配合物)Schiff base complex(席夫碱配合物)homoleptic complex(同配体配合物,单一配体)heteroleptic complex(混合配体配合物)1 总原则总原则配体配体合合中心原子中心原子(氧化数氧化数)2 配体次序配体次序中文命名法中文命名法(1)无机配体无机配体有机配体有机配体PtCl3(C2H4)-三氯三氯乙烯合铂乙烯合铂(II)离子离子(2)阴离子阴离子中性分子中性分子阳离子阳离子Co(N3)(NH3)52+一叠氮一叠氮五氨合钴五氨合钴()()离子离子(3)英文字母次序英文字母次序Co(Cl)(NO2)(NH3)4+一氯一氯一硝基一硝基四氨合钴四氨合钴()()离子离子(4)按原子数目按原子数目(少在前少在前)Cu(NH3)2(NH2OH)22+二氨二氨二羟氨合铜二羟氨合铜()()离子离子阳离子配体一例：NO+亚硝酰Fe(NO)(H2O)52+(3个未成对电子)（5）同类配体中若配位原子相同，配体所含原子的数目也相同，则将配体结）同类配体中若配位原子相同，配体所含原子的数目也相同，则将配体结构中与配位原子相连的原子的元素符号的字母顺序排列构中与配位原子相连的原子的元素符号的字母顺序排列3.3.离子型配合物离子型配合物(1)配位个体为正离子配位个体为正离子当外界离子为简单阴离子时当外界离子为简单阴离子时:某化某某化某当外界离子为含氧酸根当外界离子为含氧酸根:某酸某某酸某例例:Pt(Cl)(NH3)3Cl2Co(Cl)(NH3)5SO4(2)配位个体为负离子配位个体为负离子当外界阳离子为当外界阳离子为H+时时:某酸某酸当外界阳离子为其它阳离子时当外界阳离子为其它阳离子时:某酸某某酸某例例:H3Fe(CN)6K3Fe(CN)64.4.多核配合物多核配合物在桥联基前冠以希腊字母在桥联基前冠以希腊字母-桥联桥联n个中心原子时，记为个中心原子时，记为 n-(n为为2时可省略时可省略)(NH3)5Cr(OH)Cr(NH3)5Cl氯化氯化-羟羟十氨合二铬十氨合二铬()()(C2H5)PICu3Cu3P)5H2(C(C2H5)P3(C2H5)P3I二二(-碘碘)四四(三乙膦三乙膦)合二铜合二铜()()5.5.含不饱和配体配合物含不饱和配体配合物(1)若链或环上所有原子都与中心原子键合若链或环上所有原子都与中心原子键合,则在配体前加则在配体前加-例例:KPtCl3(C2H4)三氯三氯(-乙烯乙烯)合铂合铂()()酸钾酸钾(2)若只有部分原子参加配位若只有部分原子参加配位,则在则在-前加上配位原子位前加上配位原子位标标(1-n);若只有一个原子参加配位若只有一个原子参加配位,则在配体前加则在配体前加-例例:CH3-CH=CH-CH2-Co(CO)3 三羰基三羰基(1(1-丁烯基丁烯基)合钴合钴()()6.6.几何异构体几何异构体(1)顺反异构体顺反异构体(2)面经异构体面经异构体顺顺-反反-面面-经经-Nomenclature 英文命名法英文命名法1.The cation is named before the anion.Regardless of whether the cation or the anion contains the complex ion.2.Within a complex ion the ligands are named first in alphabetical order then the metal.3.To name the ligands:anionic ligands end in-o neutral ligands usually called the name of the molecule.Exceptions:H2O(aqua),NH3(ammine),CO(carbonyl).Bridging ligands are indicated by placing-before the ligand nameLIGANDName of Ligand in Coord.Cpd.bromide,Br-bromo or bromidochloride,Cl-chloro or chloridocyanide,CN-cyanohydorxide,OH-hydroxooxide,O2-oxocarbonate,CO32-carbanatonitrite,NO3-nitrooxolate,C2O42-oxolatoammonia,NH3amminecarbon monoxide,COcarbonylwater,H2Oaquaethylenediamineethylenediamine4.When several legands of a particular kind are present,we use prefixes to name them.di tri tetra penta hexa5.If the ligand itself already has the prefix in its name(as in etheylenediamine)use the following prefixes instead:bis tris tetrakis pentakis hexakis6.Give the oxidation number of the metal as a roman numeral in parentheses after the metal name.7.If the complex is an anion,its name ends in-ate.See the following table.Metalanionic complexAluminumAluminatechromiumChromateCobaltCobaltateCopperCuprateGoldAurateIronFerrateLeadPlumbateMetalanionic complexManganese ManganatePlantinumPlatinateNickelNickelateSilverArgentateTinStannateTungstenTungstateZincZincate8.Specifying donor atoms.The first method,the kappa()convention,is general and can be used for systems of great complexity.The second,use of the donor atom symbol,is appropriate only for relatively simple systems.9.Use of prefix for bridging ligand10.Use of prefix in any cases where the central atom is bonded to contiguous donor atoms.11.Polynuclear complexes:12.Metal-metal bonding:Simple Examples:Naming from Formula K3Au(CN)4Potassium Tetracyanoaurate(I)KCo(C2O4)2(NH3)2Potassium diaminedioxalatocobaltate(I)Cr(en)2F2NO3Bis(ethylenediamine)difluorochromium(III)nitrateFormula from Name Hexaamminechromium(III)nitrateCr(NH3)6(NO3)3 dichlorobis(ethylenediamine)platinum(IV)bromidePtCl2(en)2Br2 bis(ethylenediamine)zinc(II)tetraiodomercurate(II)Zn(en)2HgI41.写出下列各配合物或配离子的化学式：(1)硫酸四氨合铜(II)(2)氯化二氯水三氨合钴(III)(3)六氯合铂(IV)酸钾(4)四硫氰二氨合铬(III)酸铵(5)二氰合银(I)酸根离子(6)二羟基四水合铝(III)离子(7)二氯二(甲胺)合铜(II)(8)四氰合锰(II)酸六氨合铬(III)(9)三氯(乙烯)合铂(II)酸钾(10)氯化羟基氯 四氨合钴(III)二(乙二胺)合钴(III)2.命名下列各分子或离子：(1)Ag(NH3)2+(2)Fe(H2O)63+(3)CuC142(4)Pt(en)32+(5)Co(NH3)4NO2Cl (6)Co(NH3)5BrSO4(7)Na3Co(NO2)6 (8)Cr(NH3)6Co(CN)6(9)Fe(CO)5 (10)Co(ONO)(NH3)5C12练习题练习题