9 | Coordination Compounds JEEMainmuesroxe + Molecular or dion Compounds + omarion * Terminology Related to Coordination + Bonding in Coordination Compounds Compounds + Shbly of Complexes = Werner's Theory ‘IUPAC Nomenclature of Mononuclear Coordination Compounds + importance of Coordination Compounds 9.1 Molecular or Addition Compounds ‘When solutions containing two or more stable salts in simple molecular (stoichiometric) proportions are evaporated, crystals of new compounds may separate out. These new compounds are called molecular or addition compounds. 08, K,S0, + Alg(SO4)s + 2480 —> K,SO,AlsS0,) 2480 Botash alam cysts ARON + KCN —> —_RIAG(CN)) potassium angentocyanide Cooraination compounds are those compounds in which a central metal atom or ion is 5 rac stared wth Poca Coed witha fed mute of ‘groups or molecules (ligands) Theadton compound canbe ded vot css foe ee eared ‘avi ‘ther words these compounds (a) Those which Loose thei Identity in Solution ie, Double alts Sih Wolds. hese compounds Inaqueous solution these addition compounds resk down intosimperions, generally formed by uoraiion thustexhibit the properties oftheir construentfons-e,anaqueoussolution emene pecouce shee ofceinaliteCl. MgCl, 6HOshowe the properties of", Mg and simpler ions. Such addition compounds, which loose their identity in solution, are called “double salts? They only exist n the crystalline state. Some other examples of double salts are potash alum K,50,-Aly(S0,)-24H40 and Moht salt PeSO,:(NH);$0,-6H,0 () Those which Retain their Identi ‘Compounds tn aqueous solution, these addition compounds donot furnish all imple ions but instead give more complex ions having complicated ftructure eg. potassium ferrocyanide does not give properties of simple in Solution i.e., Complex990 JEE Main Chemistry 1, Pe and CN" fons but gives the properties of K* ions and complex ferrocyanide tons, [Fe(CN)g In other words, n these compounds the complex tons retains theiridentiy in the solution. Otherexample of coordination compounds are Co(Ny)JCl, KyPtCl, ete ‘Actually complexes of coordination compounds are the result of accepiance of lone pairof electrons of ligands by the empty orbitals of the metal atom orion 9.2. Terminology Used in Coordination Compounds ‘The important terms used a definea complex completely are as follows 1. Complex tons Acomplex ion may be defined as an electically charged radical which i formed by the combination ofa simple ‘aon with one or more neal molecules or one or nore Simple anions or in some cases positive groups also. fests as a single entiy and is usually indicated within, square bracket te] eg, [CulNt\J* Isa complexion, which is formed by the ‘combination offour neutral molecules ofaramonia witha simple Cu cation. Silay [Fe(CNi sa complex on formed by the combination of soe GY" anions with simple Fe cation, in iteoprussie on fFe(CNNOF™ ve {ar ions and one NO*(a positively charged ligand) ion are coordinated 10 Fe" on. the complex fon canying a positive charge ef, {cuivt is called eatonte comple, the one vith @ negative charge e, [F(CN} scaled anionic complex and the one with no charge eg. (PCLAW) is called & neutral complex. Complex ions do not give tests of thelr constituent ions 2g. [Cut] doesnot give test of Cu* or Ni Homoleptie complex have only one typeof ligands linked to the cenral metal atom/ion. eg. (CNH) ” whereas heteroleptc complex have more than one type of ligands linked tothe central metal tom/ion. eg. Kalk) Sample Problem 1 which ofthe fllowing complexes are homoleptic? INCERT Exp) (2) (CoN)? ©) [conn ch (e iCN (e vinsycch Interpret 1.0) Homoepiccompaxes have ligand of ely cone kind. 8, {CONNH) INICNI 2. Central Metal Atom or fon ‘ep complex on contains a metal ator oF ton t which Bae core molecules oronsare attached. Tiss aaneeeri comtal meal atom oF fon 1's sometimes sro oe he mucear atom. In a complex, the central woo trign bensvesasthe electron alr acceptor ot Twi ci 3. Ligands 3 Ligand lion rumounded hy a nambe of ‘anions of the neutral molecules or sometimes positively ance aaa te pe ie a po ‘attached to the central metal ion or atom through ‘coordinate bonds or dative linkage. In the formation of ee es omen oer ‘eg, in the complex ions [Cu(NH,)J" and [Fe(CN}d, NH ee es Seiccnipietaccue men cet entcity is one, HzN—CH,—CHy—NH, NH,CH;COO™ Se epee pe ee ana eee seyfemimgcnint br Depending upon the number of donor atoms (or sites), the Pete ber on tess (a) Unidentate or Monodentate Ligands ‘These ligands contain only one donor atom (or site) which ‘scapable of donating an electton pairand thus, attach 0 the central metal fon only at one point eg, CK F-,cl Br, OFF, HO, NH NO, IAN (pyridine) ere (b) Polydentate or Multidentate Ligands Ligands which contain two ormore such atoms which can simultaneously serve as donor’ atoms, are called patents or matdenat ind, Sch gan tach i the cenirl metal ion at more than’ one point Ponte Tarde wh ono dono at oe Sed bidentate, and with three, fou. ve and six donor ates are called forte tetra (or quad, penta and hese. forces demands respecte, #4 Rexaor sexCertain polydentate ligands have flexi dentate character, e, they donot use all the donor atoms to form a complex 8 EDTAIsa hexadentate ligand but tan algo act as Pentadentate or a tetradentate ligand, auton Pt Sone iS ncn bah ‘menses waes set igna ha kcoatee ces a me ns, Te Se |, elo Monto ae xt asm tr ees hoe o SX L (C) Chelating Ligands Polydemtate ligands, the structures of which permeates the attachment of wo or more donor sites at the terminals ‘of a chain to the same metal ion simultaneously, thus, ‘losing one or more rings are called chelating ligands and the compounds formed are known as chelate compounds, ‘Thus, a chelate may be defined as. ring suche formed by the combination ofa polydentate ligand having two or ‘more donor atoms at the terminals with metal fon forming part of the ring. The process of formation of chelates is called chelation. HNN NH” [ino Chelate formation Chelate complexes are more stable than ordinary Complexes in which the ligand ts monodentate. The Increased stability of the compound due to chelation i= called the chelate effect Generally the chelate complexes with five or six membered ings are more stable. Out of these, five membered rings are very stable when they involve saturated ligands, eg, ethylene diamine conteins only ‘ingle bonds and forms five membered stable ring structures. On the other hand, six membered ring structures acquire maximum stability when they involve unsaturated Coordination Compounds 991 ligands containing conjugate double bonds This is due to the resonance effects involving metal d-orbiials and ligand orbital electrons. The stability of the chelate complex is explained on the basis of entropy effect. When one end of en (ethylene diamine) is coordinated, the probabiliy of the coordination of the other end is high because this end is bound to stay lose tothe cation. This shows that it is easier to form a chelate ring than coordinate 10 two independent molecules. ‘Thermodynamically, the increased stabiliy due to chelation can be attbuted tan increase in the degree of, freedom of the system. A large entropy change but only small heat of reaction generally accompany the chelation process. The complex compound having maximum number of rings formed with the ligands, i= most stable, A complex (aen)P* is tess stable than a complex (M(EDTA) because in the former there are thtee rings while, the latter Involves five rings. Sample Prablem 2 the sabilistion of coordination ‘compounds duet chelation i called the chelate eect. Which ofthe following isthe mos stable complex specs? INCERT Exemplar © Fee © Feoort @ tracou) (@ ey, tem 09" Jee ‘complex is more stable than the other given de to chelaon (d) Ambidentate Ligands ‘There are certain ligands, which have two or more enor aims ‘but in foing complexe oly one nor stom is attached to metal ion. Such ligands sre cad ambidenate gon Some ase oe ligands are MNO» (Niro) (MONO [Nitsit) M ccN(Cyano) ‘M «= NC\socyane) ‘M&SCN{hiocyano} tones tee shame no reas ancora Snore tp pangs ‘the phenoxide ion also become electron donors. n= ¥ ‘hen on