Me 27/09/2022 Crystal field theory (CFT) + model describing the electronic structure of ‘yansition metal compounds, + accounts for some magnetic properties, colours, hydration enthalpies, and structures of the complexes. + Does not attempt to describe bonding. + Developed by physicists Hans Bethe and John Hasbrouck van Vleck (1930s) + Combined with MOT to form the ligand field ‘theory (LFT}, which provides insight into chemical bonding in transition metal complexes. + Ligands must possess one or more unshared pairs of electrons. + Aligand which can only form one bond to a central atom orion is a monodentate ( ‘one tooth’) ligand, e.g,, NH, , CN. + A polydentate (‘many teeth’) ligand can form ‘more than one bond. + Examples: = Ethanedioate ion and = Ethane-t,2-dlamine HoNCHoCHaNHy + Ethane-1,2-diamine has lone pairs on two N ‘atoms that can form coordinate bonds. + The two coordinate bonds formed by each ligand are thought to resemble the claws of a ‘rab (Greek: chele), and such compounds are ‘chelate compounds or chelates. + In the polydentate ligand, 1,2 bis{bis(carboxymethy!)amino}ethane ‘OHS, chg0 ibs ,cusi Ont ‘Hebe ethylenediaminetetraacetate), has unshared electron pairs on four O and two N atoms. The ligand forrs 6 noordinate bonds, and its complex. Jons are very stable, + Interaction between a transition metal and ligands arises from the attraction between cation M™ and-ve charge on the non-bonding electrons of the ligand. + Energy changes of the five degenerate d- orbitals are surrounded by point charges of the ligands. ‘Asa ligand approaches the M™, the electrons from the ligand will be closer to some of the d-orbitals and farther away from others. causing a loss of degeneracy.27/09/2022 + The electrons. the d-orbitals and those in the ligand repel each other due to repulsion between like charges. + Thus the d-electrons closer to the ligands will hnave a higher energy than those further away hich results in the d-orbitals spitting in enerzy. Factors affecting the splitting soups + The most common ype of complex octahedral ~ sigandsform an octahedron srourdthe metal ion, + In octohedral symmetry the doritals split into two sets with an energy difference, (the erysta-ield split parameter} where the dy, 4,, and d,,oritals willbe lower in energy than the and dz, which wil hve higher eneray, because the former groupisfarther from the ligands than the latter and therefore experience less repulsion + The three lower-energy orbitals are referred 10.25 ty and the two higher-energy orbitals as, = These labels are based on theory of molecular symmetry. Typical orital energy diagrams are given below in the section High-spin and fowspin. ++ ei + Tetrahedral complexes are the second most ‘common type; here four ligands form 2 tetrahedron around the metal ion, Ina tetrshedral crystal field spiting the d- ‘orbitals again splitinto two groups, with an energy cliference of where the lower energy orbitals will be d.#and'o,2,2 and the higher energy orbitals il be dy, and d, - opposite to the octahedral case, Furthermore since the igand electron In tetrahedral symmetry are not eriented direct towards the -orotals, the energy splitting wil be lower than In the octahedral case,27/09/2022 + Square planar and other complex geometiles can also bbedeseribed by CFT +The sie ofthe gap A between the two or more ses of otbitals depends on several factors, Including the ligands and geometry of the complex. + Some ligands always produce a small value of 8, wile others alway give a large splitting. +The reasons behind tis canbe explained by ligand Feld theory. + The spectrochemical series isan empircaly-derived ist ligands order by the sizeof the spliting & that they produce (small t large A). spectrochemical series ‘The order or ligand strength (spitting effect follows: re Bre <5® d electron transition. However, colour can arise in these species by charge transfer where an electron between the ligand and the metal, resulting in an intense absorption. + For example, copper(l) oxide, Cu,0, in which copper(!} has a full 342° subshell is red due to charge transfer. + The colours of transition metals are directly related to the energies of d= d transitions, ‘governed by the ligand field strength, 0. + This is affected by the: = pumber of gands = shape ofthe complex ~ oxidation state of the metal mature ofthe lgand + We have already seen how the number of ligands and the shape of the complex affects the colour of Cul) and Cot) complexes. + For example,27/09/2022 Py At ey fi, te ‘chet leche + The ligand field strength in a tetrahedral field, 4, < octahedral field, A, 50 the complex absorbs light of lower energy when an electron undergoes a d-> d transition. + The hexaaquacobalt(t) ion absorbs light in the blue-green (490nm) part of the visible spectrum and therefore appears as the complementary colour, pink. + The tetrachlorocobaltate(l) on absorbs light in the lower-energy, yellow region (590m) of the spectrum and appears as the complementary colour, blue. + An increase in oxidation state ofthe central metal tends to increase the ligand field strength, By, For example, the blue hexaaquachromium(i) is readily oxidised to the ruby-red hexaaquachromiumit) in aif oe-© > pan he why “The hexaaquachromium(ti) ion absorbs light in the yellow part of the visible spectrum (590nm) and so it appears as the complementary colour, blue. However, the hexaaquachromium(tIi) ion absorbs blue-green light in a higher energy part of the spectrum (490nm) so It appears a5 the complementary colour, red In general the ligand field strength, Ay ford 4 transition In octahedral complexes increases nthe order: In < NP*< CoM < Fet¥< V* < Feb < CO" «VB Co! ‘As might be expected, the higher the charge on the ‘metal lon the stronger the Interactions with Higonds in the erst fed. ‘This s the speetrochemkeal series for metal ons. LUgand substitution ean havea very dramatic effect on the colour ofa compound, “Treating the ruby-red exaaqunchromtui fon with concentrated ammonia solutions leads to the formation ofthe yellow hexaamnechanun(t fon:27/09/2022 + The hexaaquachromiumiil) ion absorbs light in the blue-green region (490m) -because of ad- d transition and so it appears red, + The hexaamminechromium(t} ion has @ stronger ligand field, so it absorbs higher ‘energy blue light (460nm) and appears as the ‘complementary colour, yellow. Why are sompaunys of tenon elements often paramagnetic? {iron is magnetic. + Most people know t ry special type of + In fact, iron shows, magnetism called‘ «The two metalgfolowing itin the firs transition Tovies, cobalténd nickel, also show this type of magnetism. «+ Ferromagnet{sm i 2 varity of magnetism known ‘3s poramognetism. «A paramagrfetic substance put lose 103 Irbenetitield willbe attracted Into the feld. + Many transition metal compounds are paramagnet It is the magnetic field associated with the spin of an electron that can give rise to pporamagnetism, However, only compounds that have unpaired electrons are paramagnetic. ‘When two electrons occupy the same orbital, they have their spins paired, and the magnetic fields cancel out. + Transition metals are paramagnetic when they have one or more unpalred electrons. + assume measurement of the amount of thelr paramagnetism, work out how many unpalred tlectrons are present. + This can be done using a Gouy balance » + An empty glass tube ls suspended betweon the jaws of an electromagnet, + Then the tube I filled with eryétals of the chemical being Investigated. ‘The magnet is switched on and, Ifthe substance Is paramagnet, the tube pulled down into the ‘Masses are placed, on the balance pan until the balance Is zeroed agaln, ‘The mass used Is a measure of the amount of paramagnetism, and therefore the number of ‘unpalrad alectrons. f wo aro to understand how thase unpalred ‘olectrons come about, we need to 1ook carefully ‘at what happans to tha d orbitals when ‘complex ion ts mada, 1027/09/2022 ne sample = The principle of the Gouy balance: is bolonced with the electromagnet off, and ‘again with it on. + The difference between the two weighings is a measure of the number of unpaired electrons in the somple. «The two complexes of ron(l, heaquaterrate(, {retHso)P" and nexacyanoferratet(Fe{CN}I, 376 both octahedral. «Te first has poremagnetism corresponding t fou" Unpaired electrons «The second is not paramagneticrithas na unpaired electrons. + Now, the election strvture When i lases two electrons it ore and #8 39 electrons «We have to arrange these sx electrons onthe energy WSelatagiam for]an octahedral complex. mi [AN BS8?. lef withthe argon igo into separate orbitals + we know tht electrons wil ine repulsion among them vwnenever possible sothat minimised. + ifwe follow this patern we shall have one electronin toch ofthe five orbitals, and one lft over. «+ Thiswill eo into the orbital of lowest eneray 1 aking sure that we tick tothe Paull principle, the {wo electrons in the. same orbital will have thelr spins aired. + Thisis the arrangement shown below. You can see that {here are four unpaired electrons, just as found from experiment. ~~ ee + In the case of [Fe(CN}gl* there are no unpaired electrons. + The only way of achieving this, and keeping the energy of the electrons to a minimum, Is. to put them as three pairs in the ty, set. + This s the arrangement shown below. * The reason why they take up this arrangement Is that cyanide lons have a larger effect on the splitting of the d orbitals than do water ‘molecules, aa27/09/2022 + The ligand field splitting is larger in [Fe(CN)g}* than [Fe(H,0)<)*. + When the gap &, becomes large, it takes more energy to put an electron into one of the e, set than it does to pair electrons in the ti, orbitals, + For fairly obvious reasons, [Fe(H,O}* is called a high spin complex, and (Fe(CN).I* a low spin complex. Transition elements in paints + Transition metal complexes are often used in paints to make many coloured pigments. + Examples of such pigments include Monastral Blue, in which copper(l) ions (3°) are complexed by phthalocyanine ligands. «+ If hydrogen atoms in phthalocyanine are replaced by bromine or chlorine atoms, the Colour of the pigment can be changed to other blue shades or various shades of green. eennee r + Titanium(tV) oxide, TIO, ~ineludes aT" ion having (ANB. no d electrons sod d transitions not possible. reflects al incident light andis write. used as the pigment for most white paints. How do the transition elements act as catalysts? + Two reasons: + Fist = have diferent enldation states, can tke prt cleevon Wansler reactions, ~ For example, adding Fel) or Felons to a mixta of peroxetsviphatelV} ons, 5,04", andlode ons, t. = Normally the esetton: 5,0,"(aq) + 2'(2q) > 250,*4aq) + Ils) (A) takes place at aconvenlent rate, can be followed. + HFaelae(it) sulphate solution Is added, the ate cof production of lodine Increases markedly because the Fe ons react with F fons: 2FeM(aq) + Bag) > 2Fe"(aq) + h(s) (8) + Felons are oxilsed back to Fe™ by 5,0, Ions: Benoa) + Sop oq) > 2g) + 250."(09) + combination of equations (2) ond (C)ahes cxignal equation, (A). ih + Fe" ons takepart in the rection and are regenerted 1227/09/202; ~ Taunt Trlammsnuatz seh seein cicada tt aot, 2507] se reel eset + Nets apd) ae ater on of pete che wh Sire enroie side ract eae nee [Providing sites at which reactions cam take place, nad » Rejeleetoanert onan tor «Ronee anateen atest [sor] sotzettetine tastes » Hreniateeoerabe nano aaeiseanaeiaes State a + Rigoei ot temas (} “Atypical Ziegler Nata a . alveneee baal that originally had only two + Sigel ne eee to ue eee available for bonding tp, the chain wil grow to great length, producing fipset0.one an0thet ene thy group and has revolutionised the manufacture of polymers. ‘the Ton. Crystal field stabilization energy (CFSE + The CFSE. = the stability obtained by placing a transition metal Ton in the erystal fed generated by ligands. + d-orbitals are split n a ligand fleld, some become lower in energy than before wrt. the barycenter = all lve orbitals are degenerate. + For example, In an octahedral case, the ty, < barycenter. 1327/09/. if electrons occupy these orbitals, the + Conversely, the e, orbitals > energy than in the barycenter and electrons in these reduces (destabilises) the amount of CFSE. «tf the splitting of the d-orbitals in an octahedral field's, he Nee ae «in the high-spin, the CFSE = (37/5 2,) (2 ocd ettive tothe paycenter BY Ts eee Shad the e, orbitals are destabilized BY Ys Oe * ablizaion bythe electrons in t= destabilizing «or example, consider the Wo eae configurations: = crystal field stabilization applies to transition » seetowespin nes five electrons 0 tig forpntamappnni iy Ts tols so the total CFSE [85x /s By = 2Ae toon ’ ayy Ponagenaliprnitl 1427/09/2022 Swat aise ‘Suet plas ‘saetepeamist yi fy |---—— ia eae aa Tabi at aa Tiger bipyamicl 15elk si 22k : ott [The chemistry of selected transition 7 ae ‘elements Strid $s . a [BP vansaiam 2 (ii) burning 14,5 from crudecil in ait. variable diddation states, on i ~The highest oxidation states occue when it; ) $0, combines'with O, in an exothermic combines withthe highly electronegative len reaction (the Contact Process): =45in the vanadate) on. dh = When zine reduces amoium varadotef “jcone. HC) the soiton changes fom yollow to, SSSpapie cree, anc eventual ole : LE, fs pe ; es i wb “the oxidation number changes i Sta Vo;(aa) 2-VO*(aq.) > Vag) > V"(ea) ens vv) vy ven va yA F yellow: blue blie-green ‘vio'et wt “ ap : le Pind the monufacture of H,SO4 Le rvatelier’s Principie 7 (the Contact Process): Aare the extrem are ovured fw + H,SOL1s thandfacturéd by oxidising’$O to $05. ‘temperatures and high pressures. ens namaste rods then conven, pr paeenirtri obtained from one of the}followings Repay s noe = otlow temperstures i uring Snr ade Y ete eptanet are ae) astasenie “icone nw . synods “—22/09/20 Catalyst (V,0g), seh * Allows compromise conditions (450°C dnd 2 atm) * An economically viable yield obtainad. *+-These two steps'each have a much smaller activation energy thari the direct, uncatalysed oxidation of 50, (see diagram). * The reaction is therefore much faster. €) SO, reacts with’ H,O produce H,S0,: SO,(e) + 4,01) > H,50,) The reaction is controlled by absorbing the H,SOQ, to form oleum, HS}. oe Onl) + HS) > 15,0,10,2 259", The oleum is then converted ints more ¥,S0, by adding H,0: H:S,0x1) + HO) > 24,5060.) + Vis'able to catalyse the reaction because it has variable oxidation states. =Filiyy, VV) oxide reacts with SO, to form $03: V,05 + $0; > V,0, +50, | The V,Osis then regenerated (a requirement for catalysis) by reaction with Og NE 1 2,0, + 0, > 2V,0, igen iy i Chromium. + Element24. + Hard but brittle + Attractive silvery appearance = coating the bripers and other bits of bicycles and * Onldation states #2, +3, 44, +5 and +6; ~Commonestarg 3 and +622/09/, = Le + Oxyanion: a -vely charged ion containing 0, Ip the +6 state, two different oxyarions formed, 255) jporange Cr,0, and the yellow, CO, Gp Srmosvardan tc 0,entKc0, + nsoluton he onanins an be eran tering the pt sce the falowing equa Cr,0,7 +H,0 2CrO, + 2H", r,0,*is formed in acidic solution, while C10," in alkaline solution (Le Chatélier). + In aqueous solution CP forms the violet {[cr(#,0),]* complex ion. + Adldic k,Cr,O, Is an oxidising agent, the colour changes from orangé to green. + Hot (Cr(H,0),}** undergoes ligand substitution reactions forming green specles. faprthe interconversion of C,6;8 3nd {Cr0_* can be shown as an equlibrium in 3 wae i Cr,0}*4 0-260." + 2H" 5 C0; + OH —2r0,4 +H (1,02 + 20H™2Cr0,2 + H,0 “= Reason wity most solutions and solids containing (C¥are green. + For example. HCI the dark-green complex ion [Cr(Hi,0),C' I} Is formed. e Aldgersions are valid and predict the same joutcom = C10, is formed in alkaline slutoh, =€h,0,*Inacidle solution. # KyCr_0y in acid solution = strong onlsing agent; ~ reduced to very stable Cr" on Uses of Cr * eal 'stainless'stee!' Is an alloy consisting of: -70KFe, S = 20% CF, 10% NI The Cr and Nin the alloy quickly form a layer composed of thelr exides on the surface of the steel when It frst comes in contact with the alr, ‘22/09/2022 pu SE Fe oxide, whichis laky and.porous, his oxide layer is tenacious and impervious to air and H,0 — protects the steel underneath. + Addition of smaller amounts of Cr to steet results in very hard alloy. used for making tools. + Cott, paperis used as a test for H,0. when dy, the papers blue which Is the colour of ankydrous CoCl,. _=Fallowing the adaltion of H,0, the [Coly0)eI*"'0n Is formed and the paper turns pink. Cobalt = Hard = Unreactive = white metal ub slightly blue appearance. © st" 56 + Forms 42 and +3 oxidation states: _yos stable +2 state. ” igs + Co™ forms the blue aqueous complex {Cotto} « = ea reduced to [Cott 0). = no simple aqueous chemistry for [Co(H;O})™*Ton. + very few Co®*compounds, due to instability. —£g,Cofy, nsttly acts with H,O to ve a Co™. + Col forms the stable octahedral pinie [Co(H,0)_}* ion. J+ Tetrahedral complexes = Eg, [Cocl*, are mostly blue. + The H,0 is oxidised in the reaction, producing ©; gas. . + In complexes with ligands other than H,0, CoM is stable.[ColH,0)gI* changes colour due to ligaiid substitution, pine Sraotnermi change (Colt), + 4c > [Coch + 64,0 takes place in CoCh,(aq,) if either a high conc. of Cr'or a high temperature is applied. fee 22/09/2022 + The enfianced stability of [Co(NH,),]* due to: = Ni being a stronger ligand than H,0, * + forms stor dave Bond + Erihanced stability of Co® with different __ligandsis the stability of (Ce(NHy)*- eefespere the E® values: : Picoltt,O)* + & DIColH,O)_)?"; E = 41.81 V [Co[NHa)e}* +e [CO(NH)I* 5 EF, (€ measures reactivity. The larger the ‘magnitude, the more reactive). Copper + element 29. ** = Redaish-gold2olbur =f : Ductile bit ~ conducts heat and sectrielty + second ony (98 + Stable #2 conounds but also +1. ‘WalPreducing agents e.g, H,0, F ions and Ag ‘metal can reduce [Co(H,0),]** > [Co(H,C*,)"*. Bit reduction of [Co(NH,)* >°[EHINH,) ‘requires much stronger reducinglagents ike Fe metal or V* ions. + Compounds and complexes of: ~a + aren orblue -or + white sot + Aqueous CuP*ilons are stable. + Aqueous Cy? idi'are unstable, — disproportionate'to glve Cu atoms and Cu?* ons: 2eu"> cu +"Cu¥22/09 e * The disproportionation of cus place in aqueous solution, + Bpy,Cu* compounds and those that are ‘Witeapble in H,0 are stable, : All the Cut 1,0. ions only takes halides are extremely insolublein + Although the Cul precipitate that forms is actually white, i always appears a brown colour due to the |; that forms at the same time. = *+ The Cut ions in Cul'are stable and do not eisproportionate because they are not in aqueous solution: * If. solution containing Cu** ions is mixed with a solution containing an excess of Fions, the f Sih yill reduce the Cut ions to Cut fons. ions are oxidised to |, 7 cure cur + eh, Cu alloys ‘cuana i maid brass. mae finging tones ~ atteactive ple: coloured aprearance all explain ‘why brass used to make rsusial nste-ments ~ harder than Gu, . uh ‘Thie Cut ions then combine with more F ions a precipitate of Cul: ut + F-> Cul ‘The overall equation: aise Cu (aq) + 2F > culls) + 44(30) * Both meta's are used in central heating systems. = Being more dele, Cu is drawn out to make the lbee . = Being nardur, biass is more suitable for tha joints, “which are made by casting or machloing. Cu anri sn make bronze, Bre is Harder than Cu and i used to make tues and edt,22/09/21 + Cupro-nickel ~ Qe ofthe alloys ued for UK coinage =: gjgeenough forthe coins te be made by stamping @ _berhar enous ores wens = The more 'slvery'Tooking he coin, ‘Percentage ofrickel in the alloy the highe Se « The analysis isqdane by adding an excess Of xi(aq ) to the mixture containing Cu”. “= precipitation. all the Cu as Cul occurs 2cu + at 20! +b juced can then be found + The ameunt off pred 3 known by titrating che resuiting mixture with ‘cone. of N2,5,05 solution. «+ The 5,03 lonssgeduce the I, back to T ions: 25,02" +>’ «= Near the end-point, the brown colour due to the |, becomes faint. ‘Analysing the amount of Cu in an. alloy +f pice of tras is cssved in 0a, Cu(OH),\s) pale blue selatinous preciptat= + Fe*laq) + 20H(aq,) > Fe(OH)(6) green gelatinous precip Shiga) + 30H(aq) > Fe(OH),(s) brown 6 gelatinous precipitate e + Mn(aq.) + 20H(aq.) > Mn(OH,(5} cream gelatinous précipitate + Cr*(ag) + 30H(aq) > CH(OH),(5)erev: gelotinous,precinitate git a + Note: ; (i) M"(aq,) repress (MIHO}F* j “e(OH), is unstable and rapidly dehydrates to form rust (Fe,0,). (i) These precipitates wil form with any _ggysce of OFF fon. ne ute aqueous NH, + CuSO, solutiin gives a gelatinous blue soluto advewl 22/09/2022