Crystal field theory (II) Octahedral complexes and Jahn-Teller effect, square planar complexes, tetrahedral complexes, ligand

field splitting parameters, high spin and low spin complexes

Introduction: The crystal field theory was developed to describe the electronic structure and the magnetic and optical properties of coordination complexes of transition metals. In this theory an electrostatic interaction between the ligands (negative charge) and the (d)orbitals of the central atom is assumed. Octahedralcomplexesand: dx2y2 and dz2 orbitals lie along the x, y, z axis while dxy,dxz and dyz orbitals lie in between the axis. Six ligands are considered as approaching along the three axis. So they interact more with dx2y2 anddz2(eg)thanwithdxy,dxzanddyzorbitals(t2g).Theenergyofegbecomeshigherandthatoft2g becomes lower (degeneracy ofthe five orbitals is lost).The energy differenceof t2g andeg is given byoct(crystalfieldsplittingparameter).Theegorbitalsareraisedby+3/5octwhilet2gorbitalsare loweredby2/5octrelativetothebarycentre. HighspinandLowSpinComplexesford4,d5,d6,d7configurations: ifoct>pairingenergyofelectrons,electronspairandlowspincomplexesareformed ifoct<pairingenergyhighspincomplexesareformed JahnTellereffect If the two eg orbitals have different numbers of electrons, this will lead to a further loss of degeneracyoforbitalsanddistortionstakeplacewhichcalledJahnTellerdistortion. JahnTellerEffectisobservedforhighspind4,lowspind7andd8andford9complexes; Thedistortioniseithernelongationoftwoaxialbondsandcontractionoffourequatorialbondsor elongationoffourequatorialbondsandcontractionoftwoaxialbonds,butgenerallyelongationof twoaxialbondsandcontractionoffourequatorialbondsispreferredthermodynamically. Squareplanarcomplexesford8configurations: JahnTeller distortion leads to tetragonal distortion of the octahedron. The extreme of tetragonal distortionisthelossoftheaxialligands,andtheformationofasquareplanarcomplex.Asthereis noligandononezaxisthedorbitalssplitfurther(seetextbook). Tetrahedralcomplexes: The splitting of d orbitals contradicts with those found in the octahedral complex. The donor atoms in tetrahedral coordination do not overlap well with the metal dorbitals, so that tet is much smaller than oct in octahedral complexes with the same ligands (tet 4/9 oct), and it is smaller than spin pairing energy. For this reason the tetrahedral complex are usually always high spincomplexes.Thenameoftheenergylevelis(t2,e)insteadof(t2g,eg)becauseTdcomplexesdo nothaveacenterofsymmetry.

 References: D. F. Shriver, P. W. Atkins, Inorganic Chemistry Third edition, Oxford University Press, 2001. James E. House, Inorganic Chemistry, Illinois Wesleyan University and Illinois State University, 2008 Catherine E. Houseecroft and Alan G. Sharpe, Inorganic Chemistry second edition, 2005. MIT, Advanced inorganic and solid state chemistry lectures. (http://www.youtube.com/watch?v=pZEjVRqe-N4) (http://www.youtube.com/watch?v=mAPFhZpnV58)