eeeenneed : 298 ixidation number of Ni in Ni(CO)4 ON. of Ni+4x ON. of CO = 0 ON. of Ni+4 <0 © ON. of Ni Go-ordination polyhedron is the spati atom. and atoms which are directly attached to the [Co(NHa)g]** has octahedtril géometry and [Ni(CO),] has tetrahedral geometry. terms in [Co(NHs), Cla] Cl are shown below ‘o-tnaon entity ys ag st OMOLEFTIC COMPLEXES exes in which central metal atom/ion is bonded to different types of ligands are known as heteroleptic example : (Coen) 2Br2]", [Cr(NH3),Cla]* ete. ATOMIC NUMBER (EAN) omic Number (EAN) of a metal ion in a complex = Atomic number of metal — oxidation state of the co-ordination number EAN = ZEON 2XONI| ymplex is formed, if EAN is equal to the atomic number of the next nearest noble gas. applicable in many cases but in some cases, it fails. IEORY OF CO-ORDINATION COMPOUNDS re are two types of valencies shown by central metal/ion in a compound : rimary (ji) Secondary primary valency is ionisable whereas the secondary valency is non-ionisable. Primary valency ssponds to oxidation number and secondary valency corresponds to co-ordination number. e.g., in complex (Co(NHg)g] Cl, primary valency of cobalt is three and secondary valency is sx. ary valency is satisfied by negative ions (anions) while secondary valency is satisfied by ligands, ‘can be neutral, positive or negative (positive in rare cases), ela ‘etal atom has a fixed numberof secondary valencies, ie, it has a fixed co-ordination mune secondary valencies are directional and are responsible for definite geometry and isomerism. ney by thick ‘ary valency in the complex is represented by dotted line (......) while secondary valet —. I cases, metal or metal ion should satisfy both primary and secondary valencies.AMBIDENTATE LIGANDS. coe Ses ‘The monodentate ligands which can co-ordinate With the’ cehtral atom through more than one site are iy ambidentate ligands. \ ine For example : ware Mano M+—Oo—N=0 Nitro’ NS ON ites 3. CO-ORDINATION ENTITY (COMPLEX ION) i co-ordination entity constitutes a central metal atom or ion bonded to a fixed number of oppositely charg ions or neutral molecules. It also represents co-ordination sphere. This part of complex behaves as one unit ands non-ionizable.: For example, [Co(NH3)3Cls] is a co-ordination entity. A positively charged complex ion or co-ordination entity is known as cationic complex. For example, [Co(NHg)¢]**, [Ni(NHg)¢]7", [Ag(NHg)2]" ete. ‘A complex ion which has a net negative charge is called anionic complex. For example, [Ag(CN) ]”, [Fe(CN)g]* etc. A complex or co-ordination entity which has no net charge is called neutral complex, For example, (Ni(CO)4], [Pt(NHg)2 Cla] etc. 4, CO-ORDINATION NUMBER The total number of co-ordinate bonds formed with the central metal/ion by the ligands or in other words, tt total number of ligands attached to a central metal ion is called the co-ordination number of that ion. For example TAg(CN)2] C.N. of Ag’ {Co(NHg)3 Clg) C.N. of Co?* [Fe(C:0,)3]°" C.N. of Fe? Note : Oxalate ion (C203°) is a bidentate ligand so one bidentate ligand should be counted as two ligands OXIDATION NUMBER OR STATE OF THE CENTRAL METAL ATOM Itis an electric charge which the central metal has or aj ‘The oxidation number of neutral ligands is taken to b to the charge on the ligand. e.g., the ON, of CI! =-1, The oxidation number of cation is equal to the charge on the cation. e.g., the O.N. of KY = +1. The oxidat®™ number of central metal atom or ion is calculated as below : () The ON. of Fe in Ky{Fe(CN) g} 4x ON. of K* + ON. of Fe +6 x ON. of CN 4x1+ON, of Fe +6 x (-1) = 0 ON. of Fe = 42 ippears to have when bonded to other ligands. zero. The oxidation number of negative ligands is or or