/ Stewotsomeram in Coorctination. = coorectivrfty_v same bet spatial wont criestatien diffeuint Steiersors 1 — J v Geometncal Optical v $< Co hams Tehahidrol | —_—— geometrical, In dehakudral complx thew G70 cts honu Gommuin * ° eq: ‘ UN oc“ "co Number of Steuowwomnnr + Number of ophical +geomenc come? ¢ - Number of cpbeal Gomer Here tfa molculs hor POS ” opacally machve @[masy* — eg NiCCOs A qe B41 - sar snuctune , me ad's et HO) A @ [mae]” 8 qe 4 Op = 0 awl” gsiO©lmaed"™ and (mA: Be) B G1 oO A a? | Cp: 2 Zifsnn 2 Sty) ee 1 Thu half & dus #0 first G comication Noti: Only for Masco for Td , ateuoisomir =2 other all cove €= 4 Squau Planer = always have POS , thus no opheal domn @ [ma] , s Ge4 Nn Op. 0 AZ _ e.4 @ mA Ge 2 8 A SW a” NA 8. 2 B A Nm~ @) m aren cn yf G3 mM. Op 0 p, ° S:3 cpbcally inacteo™ qi Op O GI any Ophically” mactveae [mAsBc]™ CH if B q-2 ‘, cas 1 ee ae ae g- 2 A Op mactve optically rmactne- cb rom « # _MA,B,C; 8, i A ay A BC ora tin bow Cn, Lo At i) i se Jove ov | 8 Ne av |e cle A c Op-2 op: Op op v re G-5 Op:2 G2 BYR? — + Facial and meridional - geomulrical_ Gonurs aguind 3 sor liganel A~ N ; {all thre: ot ad) < N fecial m*.* iG) sy"? No Ww Noe! en( Soo )e Nn, \ i N [~. ea a oN ee Op? (not possi ~ 3. la Yat? op: 2 2} mesy)” NA NN ( tu Vee oe \ qe " Ne v7 To _ Op: 4 oo N gat yd A focial meridenil ae[m(on,ceoy]” Na om ba” ql (Pane ; oO Nx 2 n—7 Se se [inceneees)" AN a A~ a, lo 8) oe ¢ he : a Ns on (aime of \ > B ly Op: 6 ee a a g-6 ae [m (AB) co)” c c B 1, \o? Br, | c G : ( ths) ( logs ) Bn, Lowe Bin, \ os Bin, | of & ~e fi~ ows mae ae | A | 8 ( 4 \~e Coie Op. op? me 7] ea re) g 8 re op? op-8 o- 543 28#(m (AP), cc} Op: Cenc opty ee rt asc cu-cie-fia (pr) Nee i & [a(en) cpancwe)” N NN ONG, |» ( \ wn WN, | a Loot Co Co! “TS wyeN on] nt on™ | TN [7S atau phically achive we ne? xo Gr 3+ Yor® 26 Structural torr O lonization onszation Teotny ci 80st» soz" [Co(ntts), SO,]_ Cc” —— [CotNHa)s SQ] 4 cr> - @) Untage iwomeriam : Ambidintal gard § (To (NH)s Nes] [cecrvtey, Seny?* @ Hgdrate leonwrum [Co (tC), CLT Cl * H2O Gc ordmation leomrri4m [corns] [aren @) @® uagand laomniam + Ccocenrel 24 § [eo (sO) 4e)] cl: 240 (Ga (CNHs) 6) bec ent at ff (pn) Hy-C- Cela Cs «NH Mes aus Oryrmodyynarnic sab} = Arenetr of ME tonal 94] EmwdT” +L ke: census men.ox1 CL iy & cm(sou © higiur ahs RY valu hugh Mi kyo — mL cruemodyrnornically, age -RTinky n AGU atoue forehion comer cg’ + cn® a aco] [eacenst + en? ae [eacen3] Foacendel+ oP tae [eacens]” rod cen);] 2x = Fedo.” prawn he [atlas Ly" +0 + apy atte of, OPP m-H2O bond arora Bde TO mow and Moe negpine fer 48 ke 1" ks 10%" 4.65 ky 10 ka? — dehohwhol.Overall seabrlitey comtamt k- ki ks x sx be - jot? kiokss ky > kn < kn] raion: (0 propbalately of siplacemnt deoucser cu sachon procercls (2) Ateric hinderance mouanes Excephon casts cwhere kn 7 ken n k - tt © [eaaad’s #1 Ca (ti20),671 + #20 2 ks Lod chose! * pe = Cedcv20),81) + #20 k [ca.crs0_8™*] * pie cbt [ca He),Br5] + HHO k [cdcro)e1 nO t= [cated Bas} 3120 In tha AUp entropy & quota unusual structural and conf igurattional chammge : ka >ks ® [Crechsode)" + bipy A [recteo), bipyT"* +240 ee [aceokbrdl ?* 4 2b0 [FecHsO). bipy]* bipy == [Fe cHcdopy)> T+ OPY fe [recebah Covpy)sT” 4240 1:0 weak {eld ligand py arong fel Ligand “nus product har-more CFSE volur ‘han frat two procuct produc 1 et rackon Afecking cally connploxes © Natu. of, metal ton Cl , af “tughoudation Atal liqgomda + od donon: “Low Guida Low oxrdahon state fe deruré on metal t) ligancl : TT acceptorsSALE of, metal ion Fora quen tigen. © 4 mn! fe" and metal maame ord” Irwin William Series alkaline tenth mtal (accorclng 10 Mz) parents car” zmq"' ma?" Fe" Zo KNIZK cua Zn" di Block Acritt® logky Bae Mg mine Ni CA Zn” ue giz + CFSE, anomalous property: ect tl ite componwnen * nrg Cu Catabo fy) CFse companaon * Ni* v but he ITO hoppers: A om eer . At r& enarget \ , ae ee overall thin CFSE Et cto quatin aur! 6 turmodynamic atabrtite « % f you Cu" commelsx, fy exnioie FTO _5 weak bord : kiruhcally faboite S Cu K 1 anorg pond duro STD sermacremealoyMabttoy aa More the bac character of ligand, more will be ts donor abililey stabilify Ore M(NHsg > M(H), > M Fe metal U elichopontive ¥ chutate effect Tcetcvsc,]"+ 4 chsnte —E Feat crn,” sano a= [cd(en).}" + 44:0 [eacu.o),7"+ 2en ks ” Ceciteeod.” + 3 ven a [cd tren] #4 Ho orcler of, acaortdy * kok ks AG rag ra negate valu. AHO comutont for all as same Cd-N bond entropy valu : £857 282 251 AG: oH-TAS fa) ash tun aa’ yy Aecond donor atom & in quater wicmttq: [ad altach pee rece p2gancrdled attach aati] Chalates m which t formu two o more Ting ax more stable shan which fo formeng ons *Mg- Seen hens | we AL ao | cholot effect mont pronounced cholo: fect 5 >6 rAmmnbud Ting ° - O° e ¢ ¢ e q -o _ Vy | ~m > dh Sm > ob San co” 1 7 ue 0 ae ie Oo 4 i atu secord © will be guatia distance Eng star testo os344 member an shamed Vf aver of the amg same bul donor cintre u difeuint 5 C~o. C-ON, cht | Sm < tom < | Sen vo SN Cu,—N~ é Hy é Nu batter comer than © [ Xo> Xn) Cy) ateric fect nckae to fu atom adjutit fo %u donor attached to donor atom or onset “vor become: weak. and Atabrtefy of complexe: diouases Cc CHs ws at cs ae Ya ces My | oy Nets tM. i atom metal ligand " i Nib | y ( So ta Ns jos ( 7 ~ ‘a Nu nf | poe / “ces Ha dis 4 WS Cis aotty eons dus to prosumer of atoms He oO g-9r° ° \ S HON reoranes enone tra atabitite] of complex — onesie fe Wacol FPO kenibe atabtti Grab and mechan! { Ea f vol & +. ___ Achvation energy tum of te wactionbility = secbstifeebon ae one or more Ligancl by anaiher ligand ALaclily Substation Reachoru in Ockahedral Complexes => rplacemmt of onc ligand by the other no change m cnrdatlion stale of thu metal ton > 7 change m coordmetion number - = Diasccrative mechamum (ike Su) 10] 420 [ tsm- x\—— (t.m] intermedia: > [Lo Nu] eckahicial rate » KELstx] - fost orca [Lett - gor a nr “ingonal brome Aquows_pyramcot L In most of tee substation wachen 1 gow torough aha mtemuciat” en . ~~ L ae Amoaclive mechanum u iv L [ugmnxI > [Nu re Nu] vee ened rau k Lome] CNul \ efor oogoncel abe ai a LeAl7t wee or called Ne KL monocapprcl Le | | ectahidron L clett Interchar 4 Mechanum > ho mtermidiak a formed atabls =S takes place mone slp without formmg a mlermcials tutead ths Lavrng and ent ering ligand exchange ma ammate Auip formeng an activated complir [Uamx]4¥—s[¥-- mee] [sin] activated complex activated complex @ on +e base of eT \f the reaction proceeds through drmocralive muchonam = all outer orbital complexes ox labrts (spa) tooo oO CLI 2 sped? If tru reacboo procs throug an > If orbitals have low lying Yc eg: ftw] - P BRLe) fl WwW) {ai a low lying vacant orortals octave nuchamam ae [erceuy) ce -@ aTTa) ate) nk aT no vacant orbital - x{mnck)” meat LA a fi) fiat a) foe Exaphons ede (HS) dttHs) dt jouw experimentally Lobite. vacamt at, urbybrdizad cabital thin a yaa labite LJ abit2 On the bo 4 crt ” change pr CFSE duomg stachon if low merse = Complex U mort Hf gam m CFSE Compler labile ¥ For lxwapm complexes orn ef metren a edtaed’ed . a arcdtgds- dred? inunt labile for high spmy complexes . cance cede gl ner t eT Oe ordn of, mokne int Nabil Uf e enters in eg orbttal complex & labitr, exapt A® CGC) ® ddd’au labitt at dtu moat labié ” both case : TTD tv gt Hs -TTD 44a. e +5 a4 4-— a ogg a foe 24 go g 3 booth A on > N" (chaage t Zaft e 6 not costly gen) antnes 7 down teu group p u tty M-L bond watrong bord \r + Aize alo MOMaKES A Aleric tepulion dicuases «| Ad 45d ou mote diffiued Squars Planar comperes undeigo substitudéem very rapiclly- Nu Li| yt a ne? Smo —} A Nu how steric effect & len Capac © pram)ane Cony exes iy pl af coreimation pambe 4 undergo aubablahon rapidly amet Te OU Meugh roam around Af g { the metal cation for entry of incorarng Nu tho Nu& will - enhanc tr removal of ent of fu ligand [nucenrs “ew cwicerncen"T cnr] i Conde CCNY] +CN” | Ni cen * went (Ni « (Any fart” (enh SF Y v ue met © change Le hee lability x [Retuony’ > 69 cwonT' > cao) labrtity * Bruno!" [oatteony* > Ligon)” — ste 1 Tank loloricty why Of undergo cuhiblatton by dimociahve mechanum 7 @ Wate exchang, Reaction s"] + Hs0 ot [MUROs ho [mewoveT+ * uy a met bord arengi * rol a cl ALO for non rramuifon elo for aramuthon ebrusl a orottal of 4d and 6d wu more diffused ade ade 64 on - hanutfion (man loc’ elrmenth Wats exchange acachon O fate m 7 bond ahengin x ¢ ol regi & ONG rob « | borel anength t omk.to8o" (fort) mutals, alkaline alkali’ has ree a _l_ same Fowelahenefh => Get Cr shows gTD 1¢ bone: become ocak Cax coi ects to8s ion stot (cu?", Cr*" qv) de tert) — mg" => 3d hamsihon me & bivalent lanthamicles tals with +2 oxidati > 1" call joie Irs" _—_——— > pe and V" = mest of, bivalent amnecta of, tte 3d hamuttion series =a, qa case FW Calmest mck ) yb. toreto (8 = cet and CoM LS) déqd® mot > hd and 6d sume au lowing in the inouastng order of . eer wate exchan ‘a arachon . mot apectes - # Orange tu fol a (a°) a mot (a?) 4a ge (a) £4L crt eRe CVS a qe" (dl) labite Au yet (2) + tnt nim (a) meet (0°) VENUE KF! &i ey re" (d°) an cut Cd") labite)@ ‘Squcion or Hycrelyse Liqainel replacia by HbO ane . 9 be cared out in acretic, bane or ruuhal muclium * Ceictic [Neubal + Liganel aaplacil by 120 * Bane ¢ gard Aiplaced by on? ACIDIC - HYDROLUS|S © Ecorse)” HO Ceo (Nels) 5H2O0*' + * XP By Ts sen” NO Not: CH, > rab « To mane) 2H a 3 faster dee Ligand over a“ “ paste_wuonowisis (Gree ractomort) i cont tnd] ff ore = v =~“ conjugate &* yal" show ap cots” act , K {Co (NHs)s ou] + Ws [cotntsls! [Cotreesy. (tH [cocntele Nes]? 4 HO acictic hnydralyso- cy" + Basic hydrolysis 6 foster “han ke>ke x In RDS FcotntsdsclT" and COo(WEy), CNH) Arong bond! dus to high chaige.HN NHs NH HANS Nis ® Sab ee et ee Ned? " 8 1% Ww | Sw nu, NHs NH. s lb ‘Tap (geomeb« p tually aquare pyramidal U Atabls a {cuxonal behaviour u net Ahown T back bending meuases the chance fo become TBP geomubyy ° Rat - ke [eo] kK: [col Creo} — oT ! Teo(nre)s ct) (or) CCo(NHs)6cU) Cotr) CH20 if con ¢ (eH0) o lange. ke Feotnts)5ct] CoH] Rat: kek role 3 7 © Le hee Le Cl NO”, CNT ( fends bai]” hos TOL of bau hydrolyse 9 ~ Teffect Nogives @ darutty to metal which a takin by Cl, CNT or NO; dicucumg «he e-danutfy fm mutal again -9 effect 1 edirutty nm rutal t Leaving group liaver ame hence rab of baie hydrolysu mounses-Teotpy cts) 4 Cc 1" do no i) 4 CCoceNy® HI" do nol have any effect 4 conc of OH amd bine “AG donot undergo bane hydrelyso C C Stemochitmury of substfuhon arackions tn Oh complere, [Colendgct VFO. [corer VT” Nr Ta nly 0. ce ids a 20, Kos Wel] “ ve L HO Cu. dome Aquos pyramidal meng Lagama « only one Ait ol, attack for meo 1 ® oN Q “i KS ) uO L trigonal ero vying plane Ny ' 4 SU |. J 7 Vy) Vy a a J vl " N \ ‘OH2 4,0 ~ VON Ly Nw B0%f “hans Fork co Suton nocd m Aq pln erie m Cane @nociabive mechanam . => moximu 90h ad in Ni SU ee Noe 7 . Y squau FB care) Pe" alway! quant planar eautty ayothesread ato oh. ee: Juloanfubion. Arachonam PE complexes aur Alower thao Niand RA ie Since as we go down mertnen .Facto: Affecting eusblabo Arachons m Aquax Planar commpleres ON of, entering igor Peru daft metal Anu dof tigamels faitir Tats of acachon 9 > BO> cO> FE @ Atene Effect | | Show ancaabye [mtermediate #57 if bulky group u attached che ral of acachon wat become loco | | eg: [pe(Pets)L ct] af, ~ fans , &P. 5 €tsP\ y NZ Pt \ eye Nt int ext? Loxto™* 0 54 waxiod ie 2xl0 | ; Lane S txto~e B4x1ore SL . me Me rat. drome G not much Itke cu © éotvent Effect The sclvent path Atplacment of, © by adlvent \f Adlvent with ‘metal ectlion trun ‘fu condbib' rab allo muaE haru- [Pt (pyece] * at lew concerranon | for squamt planar aubsblubon atachon mvolve , fu direct tte G an Moudye Mm co.ordmertion abitity of, ution mock by tha path to overall 26" sect, Aden Ox © good co-ereltnating selverk : DMso, #0, EtOH 6 ' provides enhee pats ob exchange: ky >> Kee @peor cocrettnatmng salverts : cl. ,GHe- Aterically Wncluedl aleohol . thi ras depords on “fu conemtrabon of cP ke >7 kaMecham m aqua planar > Auaty MA a Kbon occurs byanoxiahve mechanum via Mgonal bipyramidal cu Lone co hans Gomer ——> hans B 8 C B 2 8 | (ye 3’ ~B Pe eydZ Py SPN deny Qa A |" i a eae tk N OR cr AZ Ne 7 | ra | y quan pyramidal TBP Aquau pyrarudal Tintermecliccts | | L 5 Sa ‘> Ny ae [Peay KINO ee [Peay ]+x© vel \f water behaves as potential Ligand the asaction will be Meuipencimt of cy] abs = ksCPCASKT” for alternat: path . : ia = ke, [OcAgxI™ OT \f both tu pothasays occu simultamecuily at comparable rads = kiCPEASKT"4 ke (PE Asx” CYT wats » Kols cet Ask3”” ole = Ket KCNif cH U Ppreemt m lang exces ttn (1) can be takin a constewnt th hon te ce achon pscucto first orcler reacbon - Traru Gift Vigpre that © nck lost during he wrochon: spectator tigancl id auabahion of 4 ligand frame to it “ran ligand of @ hgand L promotes “fu rap 10, Caty > PRs NOS T° ,Sen > Br Ol Py > Nes > aco Nahi tdhao zaata bnbal chand, Fyen nahi phami F >O HO Server: CN; CON phool or qracceptor PY why Thaceepto ligancls have quate hor € Tv bonding Theox eo e mu" ect ? yrs axak b ae fom mo aio} fran Ah0rg, bord _ me |— [re(pgesycen (| a“ ‘a yp Bn > CLs PY” Ns ‘laf A Bb, Bos che sa" foca oe Pk ; cl Br : pt Nils DD ey nc ft} PL une uf PA a ny : 7 R ° B TiN “wis PK 7 |B Pe 7 a a’ hy a” Py Diatingeuiah hy wommg + CU and ham: KuRNAakoy TEST d Au dW) 2 trouve Xs ad d / Pe a/ nus du > cl: hors cis? 4tu N57 240 => Belf excher aachion : same auth = Jeoo affount mutable = Crow waco osteo thon self exchange asachion - Crow reachiory OM ne (necharnenn (rer) No medium acquiatdcomplexe canbe met | fable. *No bridging ligand & tnvalved. [Ey cr to etc) Tit 40. 1 euchan hamifer * Cus tag > bag @hraron oow - | Outra cheat atachon w fost? is : Sleays ecu by (eg —2 boy (0) gmer ligands approcch from ext. &q & abrieldedl by Wards bs o not ahieldud by tigemcl, & homsfen 6 foatia | wx) apm allowed homslen | tii) T- acceptor uigord & presert a ; / _ [po ent” — [rons [ea tretw) Felt) att) | No crumical chong oom oe (Fetw)) te a . 4 +8 ‘agin allowed hrams{ea fack suachion 2 tag bg homies | “Tr-acceptoe ligand b present Ligand euchons cat aitroct Felt) © Yaelf, Anes Mochon footer - 90 « 4 p+ ce uc))" ae [Feel Fe (HO J *__ [rectsol] + ee 4 Fee a m Ww 414 _. em [ae] apm allowed , 1 TT hus ataction 0 {patio7 tn) ye (OG]" ae Cor, +. € 03 J + [cona*°_.. feore a [corns wre 4 itd 4 fostes atachon ae Th — v» calts),]°——— IFUL ca AA be fm Compl (thos alow acachor ~ Se as + exokahon arquaed Wy 4M ae tuchen hamiferdl, Ecotnts)ey?*|Ccolnre)s}°ana fcotwwen)sJ” [coord] [cotton an P| Ccolprerds]* Rewon: [aotnts)s}"anct C0 Teo tsoy.land [co(Nts), [ ootens* w abower thom a (Colptundel (H.]" - WFE srt eu OXL HOS EDTA CNHs ¢ engin cn” ea A ar oat Slccording 40 spechiochurnical oem low plun & Among gee ligand acceptor ) thuo goat aiocon tru erurgy Jor th lon for weak field Uigarc pun len & Agu Apply nw concpt win nutal ion B 4arne- at Cross Mactions foatir ? ) [eocny"* roots) ee Teucnsi)®*+ [recNs)<) o pte (Fe cats) Je (Pe (NHs).] CRU (Nts)J" es Trucnte)* [ei nte))” kp kaand ky d for excifaom- Al st [PecNte).] ul) [Peceede tu) [Ru (Nts)as = (ki kas Kis )? Marcus and Hush equation | 2steric factor ( f- 4) Inner SPHERE mecHealis => bridlgr ligand mut be prevent i d A RO ont must be labile (rectuctant) and frust (ouidomt) (Rol) U1 = reacton wil be frat f Wotae? ore Og elchon hanifen (srmer lgemd vo Ru sounet of hamafr) ti) bnidging hqand has unsaturation or extencled conjugation ; = [cocnne)g ct] Cortsen fee [orcrscdgci]s [CoCHor,T" # sui? = mrchanu m: na a ) a+ ——_——— qt Jo) cr — Colts [omy + [MO \ ae e Crt) ° - Cott) core ST % . A | (arn) £5" Wilt" Ls 9 labit: a— ( Cu) an) WA (OH2), Cr cai CotNHa)<] a) | ltt) x [Cocnts), Jaf [G-(tuoy.cile mm oH mk Jwo ATA) EPA os thank labite . ['Co (NH). 0] | rapid hydrolyc (cotts0)J" + SNeTate = k Coxiclant }Catcuctant] “Anew 4 oretiy atachon * LT cocitaye x] [Crt] — [GrC49 0.x [Cott Y"+ SNH! "Xe CF Bir, 4 SCNT NCS NOF NOS SOP", Ny, POP) The larger fe size of halide fact will be the rats of araction ye PACU By cr" Adjaant and Remots Attacl Coordination + only one atom: adljacint aitacke Ceq a] coordination 46 40 deffeunt atom: armols attack (y Sen") y [cotwre, sen Ts CorcHs0),]" [fite)--Co- S— Gls] adjacent odtack [(w0),-c0)""* nes- Cr{ts0),)° x07 [cotwie), Sen) [ CrCHsO),]**§+ [lues),-@- secen-erctudds]* thi crauge) naa anal. wh \ cut) % [Cotnti) nee" + [encoun] Aoft- oft CC) ‘thus umots attack fruocrralele. | samo attack. [cocto).]"+| [sen crCus0)¢|" Boe anti — NeCeS- Cote] * aa Soft soft: area amour altackBridging Nord not homsfove of [Fecoud* 4 [eoceng}"— [ (crs Fe- en Co(ca),) ; wet naieee i (10 hydrolyis A 4 dL aL 4a tet) (abstr) [recein,]'+ [cocennstv0)]” Fe- CN bond w move ataby than N-Co bond « [incle}s Ceecusc),]"*———[(, -2r- l= Cr con]? int labile . farcen,} [ocr] Tr Cl w mudatable Fan o1 Inner aphere & Honsfer % foatia than anita reaction accusing through 0 Cura apfure muchamam- m i" om % HOMO Lumo Aeedlrdliom | * ng fi Exornpt © oy) ote) 10° cele ®@ o%e5) 1" (tg) 7 ce |B? + lot ® T(t) @o*(&) velo?! © wy) T(t) No acceleration vy" | Rut” @ c*_s6% (c-ct20). J’ ——— 10° accelrration ‘omer (It) Homo int 0 fort - 414 cofttts)s Cl) 2 Colt!) —— ae@ [crencni]"s (ruttecde]” Putt) Crt). 2 ues 0, —> te Aad Da Dome ° ‘ @ frporg”’ 4 (Coct0]™ y— Lome ty & 24.2, oet4 Queso} © Ceaceed.]* . 4 4 Domo AL A A ome en Reachon. Fotenbial Gu Curves Or Elicron Troms AG + Got fee energy ceo Agt etNe. Erurgy if Pek ArG=-ve araction -Co-ordinate Are -Ne i reaction coordinats