Coordination Compounds Coordination compounds are those molecular compounds which retain their identity in solid state as well as in dissolved state. In these compounds, the central metal atom or ion is linked by ions or molecules with coordinate bonds. e.g. potassium ferrocyanide, K,[Fe(CN)g]. aq K,[Fe(CN),] = 4K* + [Fe(CN),]* Central metal atom a Ligands K,[Fe(CN)g] «Coordination sphere (entity) Counter ion Coordination number Double Salts These are the addition molecular compounds which are stable in solid state but dissociate into constituent ions in the solution. e.g. Mohr'’s salt, [FeSO, -(NH,).SO, -6H,O] get dissociated into Fe**,NH} and SO} ions. Terms Related to Coordination Compounds 1. Complex lon or Coordination Entity It is an electrically charged species in which central metal atom or ion is surrounded by number of ions or neutral molecules. (i) Cationic complex entity It is the complex ion which carries positive charge, e.g. [Pt(NH,),]°*. Gi) Anionic complex entity It is the complex ion which carries negative charge, e.g. [Fe(CN),]*~2: Central Atom or lon The atom or ion to which a fixed number of ions or groups are bound, is called central atom or ion, It is also referred as Lewis acid. e.g. in [NiCl,(H,0),],Ni is central metal atom. It is generally transition element or inner-transition element. These central atoms/ions are also referred to as Lewis acids. 3. Ligands Ligand is electron donating species (ions or molecules) bound to the central atom in the coordination entity. ‘These may be charged or neutral. Ligands are of the following types: (i) Unidentate It is a ligand, which has one donor site, i.e. the ligand bound to a metal ion through a single donor site, e.g HO, NH, ete. (ii) Didentate It is the ligand, which has two donor sites. eg. yoo: CH,—NH, coo- CH,—NH, (Oxalate ion) (Ethylene diammine) (ox) (en) (iii) Polydentate It is the ligand, which has several donor sites. e.g. [EDTA]* is hexadentate ligand. CH,COO- HCN “\cH,coo CH,COO- H,C_NC . CH,COO- [Ethylenediamminetetraacetate ion] (iv) Ambidentate ligands These are the monodentate ligands which can ligate through two different sites, e.g. NO3, SCN”, ete. (vy) Chelating ligands Di or polydentate ligands cause cyclisation around the metal atom which are known as chelates. Such ligands uses two or more donor atoms to bind a single metal ion and are known as chelating ligands. More the number of chelate rings, more is the stability of complex. The stabilisation of coordination compounds due to chelation is known as chelate effect. [F macid ligands are those ligands which can form o-bond and x-bond by accepting an appreciable amount of x electron density from metal atom pulling facts to empty x or x -orbitals. Jee 4. Coordination Number It is defined as the number of coordinate bonds formed by central metal atom, with the ligands. e.g. in [PtCl,]?", Pt has coordination number 6. In case of monodentate ligands, Coordination number = number of ligands In polydentate ligands, Coordination number = number of ligands x denticity 5, Coordination Sphere The central metal/ion and the ligands attached to it, are enclosed in square bracket which is known as coordination sphere. The ionisable group written outside the bracket is known as counter ions. 6. Coordination Polyhedron The spatial arrangement of the ligands which are directly attached to the central atom or ion, is called coordination polyhedron around the central atom or ion. e.g. [Co(NH,),}°* is octahedral, [Ni(CO),] is tetrahedral and [PtCl,]*" is square planar. 7. Oxidation Number of Central Atom The charge of the complex if all the ligands are removed along with the electron pairs that are shared with the central atom, is called oxidation number of central atom. e.g. [Cu(CN),]*~, oxidation number of copper is +1, and represented as Cul). Types of Complexes Homoleptic Complexes Complexes in which the metal atom or ion is linked to only one kind of donor atoms, are called homoleptic complexes. e.g. [Co(NH; el: Heteroleptic Complexes Complexes in which the metal atom or ion is linked to more than one kind of donor atoms are called heteroleptic complexes. e.g. [Co(NH,),Cl,]”. Labile and Inert Complexes Complexes in which the ligand substitution is fast are known as labile complexes and in which ligand substitution is slow, are known as inert complexes.a Effective Atomic Number (EAN) This concept was proposed by Sidgwick. In a complex, the EAN of metal atom is equal to the total number of electrons present in it. EAN =Z —ON of metal + 2x CN (where, Z = atomic number of metal atom ON = oxidation number of metal and CN =coordination number of complex) An ion with central metal atom having EAN equal to next inert gas will be more stable. IUPAC Naming of Complex Compounds Naming is based on set of rules given by IUPAC. 1. Name of the compound is written in two parts (i) name of cation, and (ii) name of anion. 2. The cation is named first in both positively and negatively charged coordination complexes. 3. The dissimilar ligands are named in an alphabetical order before the name of central metal atom or ion. 4, For more then one similar ligands, the prefixes di, tri, tetra, etc are added before its name. If the di, tri, ete already appear in the complex then bis, tris, tetrakis are used. 5. If the complex part is anion, the name of the central metal ends with suffix ‘ate’, 6. Names of the anionic ligands end in ‘O’, names of positive ligands end with ‘ium’ and names of neutral ligands remains as such. But exception are there as we use aqua for H,0, ammine for NHg, carbonyl for CO and nitrosyl for NO. 7. Oxidation state for the metal in cation, anion or neutral coordination compounds is indicated by Roman numeral in parentheses. 8. The name of the complex part is written as one word 9. If the complex ion is a cation, the metal is named same as the element. 10. The neutral complex molecule is named similar to that of the complex cation. Some examples are @) [Cr(NH3);(H,0), ]Ch, triamminetriaquachromium (III) chloride Gi) [Co(H,NCH,CH,NH,), ],(SO,,); tris (ethane-1,2-diammine) cobalt (III) sulphateGit) [Ag(NH3).] [Ag(CN).] diamminesilver (I) dicyanoargentate(I) iv) K ,[Fe(CN)g] potassiumhexacyanoferrate (II) Isomerism in Coordination Compounds Coordination compounds exhibit the following types of isomerism: 1, Structural Isomerism In this isomerism, isomers have different bonding pattern. Different types of structural isomers are (i) Linkage isomerism This type of isomerism is shown by the coordination compounds having ambidentate ligands. e.g.[Co(NH;); (NO,)]Cl and [Co(NH; );(ONO)]Cl or pentammine nitrito-N-cobalt (II1) chloride and pentamminenitrito-O-cobalt (II) chloride. Gi) Coordination isomerism This type of isomerism arises from the interchange of ligands between cationic and anionic complexes of different metal ions present in a complex, e.g. [Cr(NH)¢] [Co(CN),] and [Co(NH3)¢] [Cr(CN)g] (iii) Ionisation isomerism This isomerism arises due to exchange of ionisable anion with anionic ligand, e.g. [Co(NH;);SO,]Br and [Co(NH;); Br]SO, (Red) (Violet) (iv) Solvate isomerism This is also known as_ hydrate isomerism. In this isomerism, water is taken as solvent. It has different number of water molecules in the coordination sphere and outside it, e.g. [Co(H,0),]Cl,, [Co(H,0),Cl,]C1- 2,0, [Co(H,0), Cl, ]- 8H,0 2, Stereoisomerism Stereoisomers have the same chemical formula and chemical bonds but they have different spatial arrangement. These are of two types : (i) Geometrical isomerism Geometrical isomers are further of two types i.e. cis and trans isomers. This isomerism is common in complexes with coordination number 4 and 6.el Geometrical isomerism in complexes with coordination number 4 (i) Tetrahedral complexes do not show geometrical isomerism (ii) Square planar complexes of formula [MX,L,] (X and L are unidentate) show geometrical isomerism. The two X ligands may be arranged adjacent to each other in a cis isomer, or opposite to each other in a trans-isomer, e.g. HN Ny aN t ' ‘ t ata bea cis trans (ii) Square planar complex of the type [MABXL] (where A, B, X, L, are unidentate ligands) shows three isomers, two cis and one trans. The structures of these isomers can be written by fixing the position of one ligand and Piecing other Igands trans to it. nn 11 Hentical py e.g. [Pt(NH3 )(Br)(Cl)(Py)}. Geometrical isomerism in complexes with coordination number 6 Octahedral complexes of formula [MX,L,], in which the two X ligands may be oriented cis or trans to each other, e.g. [Co(NH,),Cl,I*. trans Octahedral complexes of formula [MX,A,], where X are unidentate ligands and A are didentate ligand, form cis and trans isomers, e.g. [CoCl,(en),]. In octahedral complexes of formula [MA,X;], if three donor atoms of the same ligands occupy adjacent positions at the corners of an octahedral face, it is known as facial (fac) isomer, when the positions are around the meridian of the octahedron, it is known as meridional (mer) isomer. e.g. [Co(NHy)3(NO,)s]