Ligands: an ion or molecule capable of donating a pair of electrons to the central atom via a donor atom.
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1 Ligands: an ion or molecule capable of donating a pair of electrons to the central atom via a donor atom. Unidentate ligands: Ligands with only one donor atom, e.g. NH3, Cl -, F - etc. Bidentate ligands: Ligands with two donor atoms, e.g. ethylenediamine, C2O4 2- (oxalate ion) etc. Tridentate ligands: Ligands which have three donor atoms per ligand, e.g. (dien) diethyl triamine. Hexadentate ligands: Ligands which have six donor atoms per ligand, e.g. EDTA. Chelating Ligands: Multidentate ligand simultaneously coordinating to a metal ion through more than one site is called chelating ligand. Example: Ethylenediamine (NH2CH2CH2NH2) These ligands produce a ring like structure called chelate. Chelation increases the stability of complex. Werner s Theory: Metals possess two types of valencies i.e. primary (ionizable) valency and secondary (nonionizable) valency. Secondary valency of a metal is equal to the number of ligands attached to it i.e. coordination number. Primary valencies are satisfied by negative ions, while secondary valencies may be satisfied by neutral, negative or positive ions.
2 Secondary valencies have a fixed orientation around the metal in space. [Co(NH3)6]Cl3 Primary Valencies = 3 Cl - Secondary Valencies = 6 NH3 Coordination Sphere = [Co(NH3)6] 3- Nomenclature of Complexes: Positive ion is named first followed by negative ion. Negative ligands are named by adding suffix - o. Positive ligands are named by adding prefix ium. Neutral ligands are named as such without adding any suffix or prefix. Ligands are named in alphabetical order. Name of the ligands is written first followed by name of metal with its oxidation number mentioned in roman numbers in simple parenthesis. Number of the polysyllabic ligands i.e. ligands which have numbers in their name, is indicated by prefixes bis, tris etc, Number and name of solvent of crystallization if any, present in the complex is written in the end of the name of complex. When both cation and anion are complex ions, the metal in negative complex is named by adding suffix-ate. In case of bridging ligands: [Name of the groups to the left of bridging ligand (Oxidation state)] μ [Name of the groups to the right of bridging ligand (Oxidation state)] [Name of negative ion] Ligands CH3COO - CN - Negative Name Acetato Cyano
3 Br - Cl - F - OH - N 3- C2O4 2- SO3 2- O2 - O2 2- O 2- NH 2- SO4 2- S2O3 2- HS - NO + NH2NH3 + H2O NH3 CO CH3NH2 NO C5H5N Positive Neutral Bromo Chloro Fluoro Hydrido Nitrido Oxalato Sulfito Superoxo Peroxo Oxo Imido Sulphato Thiosulfato Mercapto Nitrosonium Hydrazinium Aqua Ammine Carbonyl Methylamine Nitrosyl Pyridine Isomerism in coordination compounds
![Structural Isomerism Ionization Isomerism: Exchange of ligands between coordinate sphere and ionization sphere [Pt(NH3)4Cl2]Br2 & [Pt(NH3)4Br2]Cl2 Hydrate Isomerism: Exchange of water molecules](/docs-images/82/85316349/images/4-0.jpg "between coordinate sphere and ionization sphere [Cr(NH3)3(H2O)3]Br3 & [Cr(NH32)3(H2O)2 Br]Br2 H2O Linkage Isomerism: Ambient legend binds from the different binding sites to the metal atom.")
4 Structural Isomerism Ionization Isomerism: Exchange of ligands between coordinate sphere and ionization sphere [Pt(NH3)4Cl2]Br2 & [Pt(NH3)4Br2]Cl2 Hydrate Isomerism: Exchange of water molecules between coordinate sphere and ionization sphere [Cr(NH3)3(H2O)3]Br3 & [Cr(NH32)3(H2O)2 Br]Br2 H2O Linkage Isomerism: Ambient legend binds from the different binding sites to the metal atom. K2[Cu(CNS)4] & K2[Cu(SCN)4] Coordination Isomerism: Exchange of the metal atom between coordinate sphere and ionization sphere when both are complex ions. [Cr(NH3)6][CoF6] & [Co(NH3)6][CrF6]. Ligand Isomerism: Different isomers of the same ligands attached to the metal. [Co(pn)2Br]Cl2 & [Co(tn)2Br]Cl2 Where, pn = 1,2- Diaminopropane tn = 1,3-Diaminopropane. Stereoisomerism: a.geometrical Isomerism: When two similar ligands are on adjacent position the isomer is called cis isomer while hen they are on opposite positions, the isomer is called trans isomer.
5 b.optical Isomerism: In order to show optical isomerism, the complex should form a non superimposible mirror image which rotates the place of polarized light in opposite direction. Valence Bond Theory: Hybridization: Find out the hybridization of central metal ion using following steps: Write down the electronic configuration of metal atom. Find out oxidation state of metal atom. Write down the electronic configuration of metal ion. Write down the configuration of complex to find out hybridization. Strong field ligands cause the pairing of electrons. Strong Field Ligands: CO, CN -, NO2 -, en, py, NH3. Weak Filed Ligands: H2O, OH -, F -, Cl -, Br -,I - When the d orbital taking part in hybridization is inside the s and p orbital taking part in hybridization with respect to the nucleus, it is called an inner orbital complex. Example: d 2 sp 3 hybridization of [Co(NH3)6] 3+ involves 3d, 4s and 4p orbital, hence it is an inner orbital complex. When the d orbital taking part in hybridization outside the s and p orbital taking part in hybridization with respect to the nucleus, it is called an outer orbital complex. Example: sp 3 d 2 hybridiztion of [CoF6] 3- involves 4d, 4s and 4p orbital, hence it is an inner orbital complex. Geometry: Coordination Number Hybridization Geometry 4 sp 3 Tetrahedral
6 dsp 2 Square Planar 6 d 2 sp 3 & sp 3 d 2 Oct Magnetic Properties: Spin: Colour: Diamagnetic: All the electrons paired. Paramagnetic: Contains unpaired electrons. Spin paired: All electrons paired. Spin free: Contains unpaired electrons. Compound must contain free electrons in order to show colour. Crystal Field Theory: Strong field ligand causes greater repulsion and thus results in the formation of low spin complexes by pairing of electrons. Weak field ligands result in the formation of high spin complexes Order of strength of ligands: CO > CN - > NO2 - > en > py = NH3 > H2O > OH - > F - > Cl - > Br - >I -?
7 Octahedral Complexes: eg orbital are of higher energy than t2g orbital. Tetrahedral Complexes: eg orbitals are of lower energy than t2g orbitals. Δt = (4/9) Δo Crystal Field Stabilization Energy: System High Spin Low Spin Electronic Electronic CFSE Configuration Configuration CFSE Octahedral Complex d 4 t2g 3 eg 1 -(3/5)Δ0 t2g 4 eg 0 -(8/5)Δ0+P d 5 t2g 3 eg 2 0 t2g 5 eg 0 -(10/5)Δ0+2P d 6 t2g 4 eg 2 -(2/5)Δ0+P t2g 6 eg 0 -(12/5)Δ0+3P d 7 t2g 5 eg 2 -(4/5)Δ0+2P t2g 6 eg 1 -(9/5)Δ0+3P
8 Tetrahedral Complexes d 4 eg 2 t2g 2 -(2/5)Δt eg 4 t2g 0 -(12/5)Δt +2P d 5 eg 2 t2g 3 0 eg 4 t2g 1-2 Δt +2P d 6 eg 3 t2g 3 -(3/5)Δt +P eg 4 t2g 2 -(8/5)Δt+2P Magnetic Properties: Complexes with unpaired electrons are paramagnetic while with no unpaired electron are diamagnetic.
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