204 Gaytal Field Theory Fig, 1.2 eect of met-unad boning: the Cr—€ bon orks reset ant the C0 tna nr eres. 0) VE ep: raed betwen fel Cr at and ‘orbit osc) NO viewpoint dal ba Cr ant febening set on he CO ean nitrogen donor of he anon igands snot surly electronegative to prvent the build of exes econ deat on sum in (ANNE wh te esl tht the complex i untble In apporen contraction 0 he cleconetalty prince there re many com: pet in wtih be mil exte insu oidaton site ad 3! onde to a Semen ofa low seeronegivny. Amon the moa prominent etanpes the trmilon ntl eartonyi arg Cat of compounds which tbe Krad (CO) ond othe ental metal ough cto. The suc of stably in these complete is thecapacty oh carbon monoid ean ace "back donation fern Sensi fom the mal stom, Within valace bond theory. Is paces can be Ses ners of sean: Gad: + er o ap ‘To whatever exient canonical form H contributes othe resonance hyd letron density wil be shied fom ehtomtur to oxygen. A me precise examination o this cess ndizates that the dlocaletion ofthe elcton densy ocr overlap of 317 ort on the metal with n oral of appropriate symmetry onthe carbon ligand. n valence bond theory. the gaa orbital would be on ofthe p ott of the cron alcon (thus making iH unavaiate for bod fo the oxygen whereas the rmokeciar orbital theory would speak in tems of overlap with The + anibonding forbial of cuban monoxide (Fg. 11.2. In ether Fepesenation & 7 bond forms between metal and fg and provides a mechanism for a shit in electron densi avay fom he meal toward the ligand. The formaton of bonds of tis type wl be Atscussed a greater enh lr ia this chapter. "The wane! hat laegaly replaced valence bond theory Yr nrpeing the chaise of coordination compounds was the erytl ld theory, Fst proposed in 1929 by Hans Bethe." Av ripnly conceived, twas a mode! based on 4 purely eestosae Cite Fld Theory 395 inveraction berween the gnads and the metal on. Subsequent modications, which ‘Began as carly as 1935 with pers by J. H. Van Vleck, allow some covaleney the lntractio, These adusted versions ofthc orgnal theory generally are ale and Seid theory. tis an ineresing feature of siete history that, liboush the evelopment of crystal snd ligand fel theories was contemporary With that of ‘valence bod theory they remained largely witha the province f sola state phy i for about 20 years. Only nthe 150s did chess hein to apply eral eld theory to transition metal complexes, ure crystal ld theory assumes thatthe ony interaction between the mets on ‘nd the ligands isan eletostai onic one withthe lipids being regarded negative point charges, Despite this catheruarenistic premise, the ther ts gue ‘cess in inerpreting many important properties of complexes. Moreover, the symmetty considerations invalid in the crystal eld approach are denial to thse ofthe moleculr orbital method. The cloctontatie mode thus serves as «2000 Inoxucton to modern theories of coocdination chemist) 1m onder to understand clea the interactions tat are responsible fr crystal or zane enc in transtin etal complote, fe neces there Rem rap of the geometrical relationships of the d ort, There eso unigue way of tepresenteg. Ate five xb, but te most convenient representations ae shown a Figs 3 ond 4 tn fact thete ae sic Wave functions that can be write or orbital having the ‘ype! fourlbed for dy ad dss, for example) esmich as there Come ony ve orbitals having any pysicl reality. oe of them fe df conventionaly regarded linear comtnation of two others the ds and do, Thus these ate ‘wo orbitals have no independeatenserc, but the dan be thot eas having he average properis of the two (Fg. 3h Therefore, ince tath hare high election seosity slong the = axis, the ds obit has a large fraction of is cectton dens ‘encentatet slong the sare ais. Alo, since on af the component Way anes (dz_,) has bbe along the ans andthe ther) along they thereat «4 orbitals atoms of electron density inthe y pine, Thi. component, which ‘en refered to 382 "daughnat” or "ella i frequently neglected in petrel ‘epresenlations, especialy when an atemptibeing made fo portrayal ve orbitals Simataneously. Nevertees, itis inortat to remember hi 1 sement of the ds ov “The five dosbtls nan isolated, gaseous metal fon are dezenrale fa spherically symmeti ld of nepatvecharses paced around the metal theories wl mae segenerte butler willbe ised in energy a esl the epson between "Van Vick 3H: Chem Ph 36,106, HA the premise tthe ater is mene ee, for chample, Scher, HL. Gemma, Bet ‘roca hw acc New Yep teh xe “acon te es eae th pre rs el hor detrei hey ef hin sot i ae tl the same ine ering to a moi el remen compen "The cylin of bing te rrp coe rm fe 9s oe 95 ssc a fulmen 1.) Chem ine 9 Se IMT eee aafd Mognetiom ae ae oe | Fig. 11.3 Sia sransenent of the fre dei Fig 1 en ry sts ‘ao, Repatice wh person rbd rn Te tages erst instr Haye B,J Chem Ee BO 16 Crystal Field Effects Field Theory 397 Se" Fig. 115 Reprsenatin of ne dp orl ase combination 0.8804 422 (ale The el cay shotand stato dn the negative eld andthe negative elton inthe ort Mf the eld ests rom he inence of eal isaads (her anions or the negative ends of dpa an ach 5 [NHyor HO), the symery ef the eld wil be less than sperial and ihe deeneracy ff the doxbitls wil he removed. 1 tis splicing of orbital energies and is onseubences tate atthe ert of tl Bel! theory. ‘Let us somider rst the case of sx lisse forming an octakedal complex. For nvenionce, we muy regard the ands as beng synetiallyposoned slong he ‘tes of Cartesian coordinate system withthe metal on at Ie origin as sbown i Fi TL Asin the case of apherical Bel ll ofthe arias wil be raised in enesy ‘eative to the fce ton Bocuse of nepative charge repulsion. However, it should be Pictorial obvious tatoo al ofthe orbitals wil be afestd 1 the same extent. The ‘rbvtals ving alge axes the dad the dy) willbe mae stony repelled han the orbitals wth lobes directed between he ate dy dy atid). Ted oebitls fe thus spi ita two sels withthe do and dp» a 4 Bigher ancy hum the oer Fig. 1.8 Competes of ‘ork in a octet! gan Tee oa area8 11- Coordination Chemisty: Sonding 5 three. Division into these two groups arises ftom the symmety properties of thet orbitals within a oelahodral environmen, which We cam confirm by refering © the character tablefor ti, pont eoup (Appendix D). We see that te ds add ‘orbital trator the &, fepresentaion a the dd ad, orbitals ansform 45 the T, representation, Our ealerconelusion th tk orbitals are sl ino two Sess one doubt degra andthe ther ply degenerates thar substantiated. Te lakes customary given to these two groups ao denote these symmetry properics ‘a, ov the ply degenerate set and, for he doubly degenerate pur, th lower case ‘ing sppeorit or vals, OF coure asymmetry analysis doesnot ll os which of the ma sts of ovis higher n enegy, To deternineceltive orbital energie, te ‘ture ofthe inerctons ving ee 1 the epiting mus be conde The exten to which theo and, eri are seared in an octaedral complex is denoted by tbe 6 eubeotsigiying Oetiker) or IDDg (Fig. 117) More inspht ito the nature of di epliting can be ebizined BY viewing formation of complex ex a two-step process. In the fst step, the ligns approach the central ‘meal. prowling hypotelcal spherical eld which repels ofthe a rb othe Sune exien. im the secon the iinds eke. an Octunedal ei whic sp se ‘bial degeneracy. In going from the Rs othe seco step. we id that the bar) eler, “cenerof gas.” ofthe ovals remains constant. That is to say, the nergy fal othe eras wil be aed bythe repulsion ofthe advancing gatas Sep oe, but merely seatangng the gas fom a hypothetical spherical fed oan vtahedeal fel docs oot ler he average energy ofthe Sve doris. To maintain the constant baryeenter, iss necetary forthe two e, rial tobe further repelled by 06d, whe the thes, ona are sind Lo Sn extent of 0, as showa im Fig. 111. This constancy of the baryeente ofthe doris hots frail complexes, repardets f geometry © “Toain some appreciation for he magnitude of 4 and how it may te measured, Jet us consider thea! complex, (T4H,0),). This ion ei in equeous solutions ot “TP and gives rie ta purple color, The sale delet in he comple wil ecupy Fig. 11.7 Soing of he fred ots y ruta fe eter he 1009 TE nl inc Tat i Hy ery re pete orale aamstach i, 1 tet Swing eee al ra eon apache inc One strand nin brn he metal a ade rio tsi et a ser ome ems mt te cen Woe ‘Sabian seme umes tole al tae cece sae ing gu congas Stobilization Energy Cpa Fld Theory 299 the owes ny il silo on he ve pnt oa “The purple color isthe rest of absorption of ight and promotion ofthe, ctron to thee, ee The tan ne esd a et — Bet ‘he shoo sin of Th. 1) ht hi rson oc wa marian ot 2.3 on whch soaps et ma en 43,7By compan te bepon toute eh oat gees) 6 1 0538 mal These ae pa ef ade san ea mite ate cg of chica bod The dca the ample pone Beane te shee special tanson scent th sca eh ier teen he yt ls or hee fener sialon, decor eect ntrcom ne ain scot ae Sista bones somes mre imal The trope meas es cx om pge 1 a lig Ine case cused ove, the electron oeupies orb, which hasan energy ‘of 0s, relive co the barycenter ofthe dort. The complet can thas be sid 0 be stablied toe extent of 0.4, compared tthe hypothe sphereal eld ease L Fig. 1.8 blecrnie pect of 0. M vanes solaion of THH-OM”. The tera the lap iatet the clos sci wt purtns of th Wate scr [Prom hima, He Siler Hn 2 A he, 3 1-1 ape "tics the reer ey eens hy mens ot peop coments