Chapter - 5 Coordination Compounds
Chapter - 5 Coordination Compounds
Chapter - 5 Coordination Compounds
DEFINITIONS: o COMPLEX COMPOUNDS: The compounds in which ions or molecules (called ligands) are coordinated to the central metal atom or ion are called complex compounds. o COMPLEX ION: An electrically charged species formed by the union of a central metal ion with two or more ligands is called a complex ion. It may have a positive charge or negative charge. o CATIONIC COMPLEX: A complex which forms positively charged complex ion in solution is called cationic complex. Eg: [Cu(NH3)4]SO4 [Cu(NH3)4]+2 + SO42 o ANIONIC COMPLEX: A complex which forms negatively charged complex ion in solution is called anionic complex. Eg: K4[Fe(CN)6] 4K+ + [Fe(CN)6]4 o LIGANDS: The ions or molecules which can donate one or more pairs of electrons to a central metal atom or ion in complex are called ligands. o TYPES OF LIGANDS: MONODENTATE LIGAND: The ligand which is capable of donating only one pair of electrons to the central metal atom. These may be neutral molecules or negatively charged or positively charged. NEUTRAL LIGANDS: FORMULA :NH3 : CO :NO H2O: C5H5N: NAME ammine carbonyl nitrosyl aqua or aquo pyridyl NEGATIVELY CHARGED LIGANDS: FORMULA X : CN :SCN SCN: :OH NAME halo cyano thiocyanato isothiocyanato hydroxo 2 2 :O2 :O :NO2 : ONO :NO3 :NH2 peroxo oxo nitro nitrito nitrato amido :NH 2 :S 2 CO3 2 : SO4 2 : SO3 2 : CH3COO : imido sulphido carbonato sulphato sulphito acetato POSITIVELY CHARGED LIGNADS: FORMULA NO2 + NO + NH2-NH3+ H3O + NAME nitronium nitrosonium hydrazinium hydronium BIDENTATE LIGAND: The ligand which is capable of donating two pairs of electrons to the central metal atom. a. ethylenediammine (en) b. oxalate (ox) c. glycinato (gly) d. dimethyl glyoxime (dmg) H3C C C CH3 H2C CH2 H2C NH2 O=C O : || || | | | | HO N: :N OH H2N: :NH2 O=C O : O=C O : TRIDENTATE LIGAND: The ligand which is capable of donating three pairs of electrons to the central metal atom. a. diethylene triammine(dien) b. 2,2,2-terpyridine (terpy) c. iminodiacetato ion H2N NH2 O = C O: :O C = O N N | | | | H2C CH2 N H2C CH2 | | H2C NH CH2 N H POLYDENTATE LIGANDS: The ligand which is capable of donating many pairs of electrons to the central metal atom. a. triethylenediammine (trien) b. ehylenediamminetriacetato ion c. EDTA (ethylenediammine tetraacetate) H2N NH2 CH2COO: CH2-N | CH2 CH2COO: | HN CH2COO: CH2 O O O || O || C N | CH2 | CH2
C CH2
N C CH2 | || C CH2 O O || O
WERNERS THEORY OF COORDINATION COMPOUNDS: Alfred Werner proposed the theory Postulates of the theory are; 1. A metal possesses two types of valencies: viz, primary valency and secondary valency 2. The primary valency of a metal is variable & corresponds to its oxidation number (charge on metal ion). The secondary valency of a metal is fixed & corresponds to its coordination number. 3. The primary valency of a metal is satisfied only by negative ions. The secondary valency of a metal is satisfied either by negative ions and/or by neutral molecules which act as ligands. 4. Secondary valencies are directional and these give a definite geometrical shape to the complex. SIDGWICKS ELECTRONIC THEORY: According to Sidgwick, The ligands donate electron pair (or pairs) to the central metal atom or ion and form a number of coordinate bonds with the central metal atom or ion. Eg, In the formation of cuprammonium ion, each of the four NH3 ligands donate an electron pair to the Cu+2 ion forming four coordinate bonds. H3N NH3 +2 +2 Cu Cu+2 + 4 :NH3 H3N NH3 EFFECTIVE ATOMIC NUMBER (EAN): The total number of electrons around the central metal ion including those gained by coordination of the ligands is called the effective atomic number of the central metal atom in the complex. It is calculated as; i.e, EAN = Z X + Y, where Z = Atomic No. of the metal X = No. of e lost in the formation of ion Y = No. of e donated by ligands. EAN Rule: A metal atom or ion continues to accept electron pairs from the ligands until the total number of electrons around the metal atom or ion in the complex becomes equal to the atomic number of the nearest noble gas. NOMENCLATURE OF COORDINATION COMPOUNDS: According to IUPAC, name of complex should give information about; a. Number of ligands: The prefixes like mono, di, tri, tetra, penta and hexa are used to indicate the number of ligands 1, 2, 3, 4, 5 and 6 resply. The prefixes like bis, tris, tetrakis, pentakis and hexakis are used to indicate the number of complex ligands. b. Name of the ligand: Names of negative ligands end in o. Names of positive ligands end in ium. Neutral ligands have either special names or named as it is. c. Name of central metal atom/ion: In neutral and cationic complexes the name of central metal atom or ion remains the same. However, in anionic complexes, the name of the central metal atom ends in ate. d. Oxidation state of the central metal atom/ion: Oxidation state of central metal atom/ion is indicated by Roman numbers 0, I, II, III, IV, V and IV etc in parenthesis. NAMING OF IONIC COMPLEXES: If the complex is ionic, the cation is named first & then the anion. NAMING OF NON-IONIC COMPLEXES: Non-ionic complex is named as one word. ISOMERISM IN COMPLEXES: o IONISATION ISOMERISM: Complexes having same molecular formula but furnish different ions in solution are called ionisation isomers & the phenomenon is ionisation isomerism. Eg; [CoBr(NH3)5]SO4 and [CoSO4(NH3)5]Br are ionisation isomers o LINKAGE ISOMERISM: Complexes having same molecular formula but differ in the mode of attachment of the ligands to the central metal ion are called linkage isomers & the phenomenon is linkage isomerism. Eg; [CoNO2(NH3)5]Cl2 and [CoONO(NH3)5]Cl2 are linakge isomers o HYDRATE ISOMERISM: Complexes having same molecular formula but differ in the number of water molecules present as ligands or as water of hydration are called hydrate isomers & the phenomenon is hydrate isomerism. Eg; [Co(H2O)6]Cl3, [CoCl(H2O)5]Cl2.H2O, [CoCl2(H2O)4]Cl.2H2O and [CoCl3(H2O)3].3H2O are hydrate isomers. 2
CH2
C N | CH2 | CH2
C CH2
N C CH2 | || C CH2 O O || O
CH2
C N | CH2 | CH2
C CH2
N N H C CH2 | || C CH2 O O || O How many coordination sites present in ethylenediamine? Two Define coordination number. The total number of coordination bonds formed by monodentate ligands with a central metal atom or ion in a complex is called the coordination number of central metal. What is the coordination number of iron in (a) potassium ferrocyanide (b) potassium ferricyanide? Coordination number of iron in potassium ferrocyanide and potassium ferricyanide is 6. What is a cationic complex? Give an example. A complex which forms positively charged complex ion in solution is called cationic complex. Eg: [Cu(NH3)4]SO4 [Cu(NH3)4]+2 + SO42 What is an anionic complex? Give an example. A complex which forms negatively charged complex ion in solution is called anionic complex. Eg: K4[Fe(CN)6] 4K+ + [Fe(CN)6]4 What type of ligands satisfies the primary valencies of a metal ion? Only negatively charged ligands can satisfy the primary valencies of a metal ion. What is primary valency of a metal ion? Primary valency of a metal ion is its oxidation state. What is secondary valency of a metal ion? Secondary valency of a metal ion is its coordination number. Give the primary & secondary valencies of (a) copper in cuprammonium sulphate (b) iron in both potassium ferrocyanide & potassium ferricyanide. Primary & secondary valencies of copper in cuprammonium sulphate is 2 & 4 resply. Primary & secondary valencies of iron in potassium ferrocyanide is 2 & 6 resply. Primary & secondary valencies of iron in potassium ferricyanide is 3 & 6 resply. What is the coordination number of the metal ion if the complex ion has (i) square planar structure (ii) octahedral structure. (i) 4 (ii) 6 What is the oxidation state of nickel in nickel carbonyl? zero What type of ligand satisfies (a) primary valency of a metal ion (b) secondary valency of a metal ion? (a) Only negatively charged ligands can satisfy the primary valencies of a metal ion. (b) secondary valency of a metal ion is satisfied either by negative ions or neutral molecules. 4
diamminediaaquadichlorocopper(II) hexaaquairon(III) chloride hexaamminecobalt(III) hexanitrocobalt(III) ammonium trioxalatocobaltate(III) potassium pentacyanonitrosylferrate(II) sodium ethylenediamminetetraacetatonickelate(IV) monobromobis(ethylenediammine)nitritocobalt(III) ion pentaamminenitroplatinum(IV) ion tetraamminedichlorocobalt(III) chloride pentaamminechloroplatinum(IV) chloride triammineaquadinitrochromium(III) nitrate tris(ethylenediammine)cobalt(III) ion triamminetriaquachromium(III) chloride ferric hexacyanoferrate(II) sodium trioxalatoferrate(III) potassium hexafluoroplatinate(IV) 5
b. tetraamminecopper(II) ion d. potassium hexacyanoferrate(II) f. ammoniumtrioxalatocobaltate(III) h. hexafluoroferrate(II) ion [Co(NH3)6]Br3 [Cu(NH3)4]+2 [Cr(OH)(H2O)3(NH3)2](NO2)2
i. tetrakis(pyridine)platinum(II) tetrachloroplatinate (II) [Pt(C5H5N)4][PtCl4] 30. What is (a) an inner orbital complex (b) an outer orbital complex. A. (a) If inner d-orbitals i.e, (n 1)d orbitals are used for hybridisation along with outer ns- and nporbitals, then complex formed is called inner orbital complex. (b) If outer d-orbitals i.e, nd-orbitals are used for hybridisation along with outer ns- and nporbitals, then complex formed is called outer orbital complex.
2. A. 3. A. 4. A.
5. A.
HN NH H2C CH2 Calculate the EAN of the central metal in the following: a. [Ni(CO)4] b. [Cu(NH3)4]SO4 c. K4[Fe(CN)6] a. [Ni(CO)4] EAN = Z X + Y Where, Z = 28, X = 0 and Y = 8 EAN = 28 0 + 8 = 36 b. [Cu(NH3)4]SO4 EAN = Z X + Y EAN = 29 2 + 8 = 35 c. K4[Fe(CN)6] Where, Z = 29, X = 2 and Y = 8
d. K3[Fe(CN)6]
EAN = Z X + Y Where, Z = 26, X = 2 and Y = 12 EAN = 26 2 + 12 = 36 EAN = Z X + Y Where, Z = 26, X = 3 and Y = 12 EAN = 26 3 + 12 = 35
d. K3[Fe(CN)6]
7. A.
Explain with an example for (a) ionisation isomerism (b) linkage isomerism (c) hydrate isomerism. IONISATION ISOMERISM: Complexes having same molecular formula but furnish different ions in solution are called ionisation isomers & the phenomenon is ionisation isomerism. Eg; [CoBr(NH3)5]SO4 and [CoSO4(NH3)5]Br are ionisation isomers LINKAGE ISOMERISM: Complexes having same molecular formula but differ in the mode of attachment of the ligands to the central metal ion are called linkage isomers & the phenomenon is linkage isomerism. Eg; [CoNO2(NH3)5]Cl2 and [CoONO(NH3)5]Cl2 are linakge isomers HYDRATE ISOMERISM: Complexes having same molecular formula but differ in the number of water molecules present as ligands or as water of hydration are called hydrate isomers & the phenomenon is hydrate isomerism. Eg; [Co(H2O)6]Cl3, [CoCl(H2O)5]Cl2.H2O, [CoCl2(H2O)4]Cl.2H2O and [CoCl3(H2O)3].3H2O are hydrate isomers. 8. How many Cl ions can be ppted by adding AgNO3 solution to CoCl3.4NH3? Give reason. A. One Cl is ppted by adding AgNO3 solution to CoCl3.4NH3 which is having the formula [CoCl2(NH3)4]Cl and in which out of three Cl ions, two are satisfying both primary valency & secondary valency of the central metal ion and other one is outside the coordination sphere to fulfil the remaining primary valency of the central metal ion. 9. Give a test to distinguish between [CoBr(NH3)5]SO4 and [CoSO4(NH3)5]Br. What kind of isomerism do they exhibit? A. The aq. soln. of the complex [CoBr(NH3)5]SO4 when treated with a solution of BaCl2 gives a white ppt of BaSO4 indicating that SO42 ion is in ionic sphere. But will not give ppt with AgNO3 solution as Br is not in ionic sphere. The aq. soln. of the complex [CoSO4(NH3)5]Br when treated with a solution of AgNo3 gives a pale yellow ppt of AgBr indicating that Br ion is in ionic sphere. But will not give ppt with BaCl2 solution as SO42 is not in ionic sphere. These are ionisation isomers. 10. Why is potassium ferrocyanide complex diamagnetic? A. In potassium ferrocyanide complex, K4[Fe(CN)6] the unpaired electrons of central metal ion Fe+2 are forced to pair in the presence of strong CN ligands. Hence, there are no unpaired electrons in the complex & it is diamagnetic according to VBT. 11. Why is cuprammonium sulphate complex paramagnetic? A. In cuprammonium sulphate complex, [Cu(NH3)4]SO4 the one unpaired electron in 3d-orbital of central metal ion Cu+2 is excited to one of the 4p-orbitals in the presence of strong NH3 ligands. Hence, there is one unpaired electron in the complex & it is paramagnetic according to VBT. 7
Thus, NC 2 3 1. K4[Fe(CN)6] molecule with d sp hybridisation has octahedral structure. 2. The complex has no unpaired electron, hence it is diamagnetic. 5. A.
Write a note on inner orbital complex and outer orbital complex. INNER ORBITAL COMPLEX: During the complex formation, if the d-orbital involved in hybridisation belongs to the inner (n 1)d-sub shell, then it is called inner orbital complex. Eg: hexacyanoferrate ion [Fe(CN)6] 4 At. No. of Fe is 26, its ground state electronic configuration is [Ar] 3d6 4s2.The configuration of Fe+2 is [Ar] 3d6 4s0. 3d 4s 4p +2 Fe [Ar] CN being strong ligands, force the unpaired 3d-electrons to pair up. The resulting vacant two 3d, one 4s and three 4p orbitals of Fe+2 ion hybridise to give six equivalent d2sp3 hybrid orbitals. These six d2sp3 hybrid orbitals of Fe+2 ion overlap with filled orbitals of CN ligands & form six coordinate bonds. 3d 4s 4p Fe+2 [Ar] d2sp3 hybridisation 10
4s
4p
The complex has no unpaired electron, hence, it is diamagnetic. OUTER ORBITAL COMPLEX: During the complex formation, if the d-orbital involved in hybridisation belongs to the outer nd-sub shell, then it is called outer orbital complex. Eg: hexafluoroferrate ion [FeF6] 4 At. No. of Fe is 26, its ground state electronic configuration is [Ar] 3d6 4s2.The configuration of Fe+2 is [Ar] 3d6 4s0. 3d 4s 4p +2 Fe [Ar] F being weak ligands, are unable to pair up the unpaired 3d-electrons. Hence, one 4s and three 4p and two 4d-orbitals of Fe+2 ion hybridise to give six equivalent sp3d2 hybrid orbitals. These six sp3d2 hybrid orbitals of Fe+2 ion overlap with filled orbitals of F ligands & form six coordinate bonds. 3d 4s 4p 4d Fe+2 [Ar] sp3d2 hybridisation 3d [FeF6] 4 [Ar] sp3d2 hybrid orbitals The complex has four unpaired electron, hence, it is paramagnetic. 4s 4p 4d
11