18 Kalyani Unified Chemistry (Inorganic Part.) (sp) or square planar (dsp), Ni-atom must make available 4s-orbital for ligand electrons, This jg attained by pushing 4s electrons into 3d subshell by CO ligands. As a result, we get tetrahedral structure with no unpaired clectrons. The complex is thus, diamagnetic. It is in agreement with experimental results. On the other hand, if we consider the complex as square planar (dsp), there will also be no unpaired electron. But it is known that this complex has tetrahedral structure. This js a limitation of V BT theory that magnetic properties are unable to give true geometries of complexes, (ii) Consider the formation of [ZnCl4]?-. The atomic number of zinc is 30 and jts configuration is... 4s3d!°. The geometry and magnetic character is shown below : ze: TAL TAL] ab] blab Ground state ion | sp? = Tetrahedral 1 geometry Diamagenetic zee LAL [AL | AL] ab |b C. Square planar complexes (a) Consider, [Cu(NH3)4]2* iva. In this complex, the oxidation number of Cu = + 2, According to Hund’s rule, the numter of unpaired electrons in d-subshell of Cu?* ion = one. In order to accommodate four electron pairs donated by four : NHs ligands, four vacant hybrid orbitals ie., must be made available. For cither of three possibilities, Cu2* ion must make available four orbitals for ligand electrons. 3d 4s 4p Ad socustioal [ALLIL ALP ALIAL] [4 route toed [ALL ARLAL PAR A | LAb) (bab AL Ss He NH NHs NH3 possibilty oS sp? HYBRIDISATION [Cu(NHs)4)** [18Ar] ‘Second possibilty [Cu(NHs)<]* [18Ar] Third possiblity — ‘sp¢d HYBRIDISATION (a) sp?-first possibility (b) dsp?-second possibility. (c) sp2d-third possibility. First possibility (sp). Since there is no vacant d-orbital availabl idi or s eae ane le for hybridisation in Cl ion, sp3 hybridisation i, tetrahedral geometry is expected. The number of available unpaired electrons in the complex is one. Thus, itis paramagnetic due to one unpaired electron, It agrees Witt experimental magnetic susceptibility results, : Second possibility (dsp). X-ray analysis indicates that thi i ‘ sis his complex ion has square plan geometry. Thus Cu?* ion must be dsp? hybridised. This is possible aay if one of te 3d electrons