10.13.3 Hydrogenation of Olefins by Wilkinson’s Catalyst Ithas been already mentioned (cf. Sec. 10.12.11) that the metal complexes can activate Hy either by the favoured homolytic H—H bond cleavage (i.e. oxidative addition leading to the hydrido complex) or by heterolytic HH bond cleavage. Hydrogenation of olefin is thermodynamically quite feasible but the process does not go on without any suitable catalyst. H,C == CH, + H) —> HjC—CH,, AH? = -136 kJ mol", AG® = -101 kJ mol" (at room temperature) To favour the process kinetically, it needs activation of both H; and olefin. Among the different metal complexes, Wilkinson’s catalyst is quite efficient in hydrogenation of different types of alkenes at a Partial pressuse of H, close to | atm or less. The mechanism of catalysis by this catalyst has been explored in detail by Wilkinson and coworkers and Halper and coworkers; © scanned with OKEN Scannert cz F a = centres ot Wilkinson tis 00's cat Ces tin Te at rea + eynodiui() is 8 16e-compeang Any come il Gets enaton Eatin pe oe ively wnsaturation and pos Goris cn ee oan ny Hen a Ty cao pn ses Wi ts a re ld RC) compel ination io fs ipa ge sis cag ag mnt ile. This Square planar Wy ean ase a ot eatalyts BY WIKingons eating on isan lg 08 curd onan Li pe susie phosphine Heals dissin rorotil ipods Gaosaee EPS ‘RhCI(PPh),]=[RACI(PP, e s)y] + PPhysK, =Laxt0% use) hia \] tg 14x10 mola? seo the insabily of 14-comples, its pecaus Traintain the 16e count een suggrted thatthe dso pis sins nated me: 4 co Nove me A cts a Seca eee ans sis dissociated product, [RKCKLAS)] or RACHL i te ave cat ané et cont ce IRKCHLs] may be dserbed aa alas rere compe ridences in favour of cssociation ofthe subtitatd phosphine rm he Pers complex ms ie eaalt: The ec vient spats iv sc arate the et) Te igand isoraon foe sarin es seca) sae oeeeratin) fe stating cope case ined bse ea. EP), then the catalytic efficiency disappear “The alkyl phosphine ligand also bis Oo Srongly than PhP. (i) If the process started wih cog i ‘where the “lr—P" bond is mc! RP bodhen the calls GPP eee etl geet te aie call indy suppor that the isoiasonofptsrie 1 os (Note: There are kine rcs ath sig oe ARO TTT ae ee ae eae ee TS ee ala ate Pence an oxidative ation: © scanned with OKEN Scanner1610 enous Cacers oF NOBOANE CrEusy GD eer » Ee EL (a cissiinydride complex) Cristom sanentin: ya + Hy —P et eN, ie oe ™ ! 0 0 Note: © Ifthe icootnte species [RCI] Le. uascvaed species scomsieed te ate catalyst, then the step canbe represented as follows: en ene mess — vs i oy ce the oxidative addition very ‘eTe stating comple (witout sociation of can enpeience he oruve slowly (a. 10" slower) ears in umn le caer ere ie jlecule, Presence of the so many the plement of solvent moh PPh (weak r-aceptoPigand) makes th Rl) cente quite tail «16 (186 ote eatlyss is anumed proceed irogh ine msl speci, then his stepmay beeps a follows ono Me (08) © scanned with OKEN Scannersmo 1€ REACTION Pave: Rcy ge hee Cero Lee eve must Be Of aPPTOPFa size, Hig Crag a oi ighy steri ty 1 200 is is Upset aly crowd 08% cat fg coordinated hydride ligand ‘Alten congo, at Migration 1d to the alkene e¢ the ir Jot ote ride team ordinaed 0 it cis pop eR Hs Mnyarige(eceribed 38 the migratory ines ston My 85 ean alkyl complex and hs sey eat 20 ora aig et ci 0 re re ete (st io insertion reaction may be simply presented M-H +R,CmeCRi—> McRae cess probubly pases though a four membered yt tanion state yo alkene it 20 spe id hndmagen migratory insertion reaction ithe a tenn ep. is evel Tr Hy the rate is much faster than that for Ds fet (a verve efimination of alkane and regoeraton ofthe active clays: ee CHR u 8 a Ge om) tare) (fete eas on stat eating the ‘This reductive elimination oceurs through a three membered cyclic transition state ing ‘eafer of the metal bound hydrogen to the C-atom of the alkyl group. ‘The catalytic eyele is shown in Scheme 10.133.1. © scanned with OKEN Scanneray L—rh'_L (Precursor catalyst) a (16e) -s||+s. aft th es le L—Rh—L L—Rh—L (cis-compound) (oxidative a estes a | (Active Catalyst) (186) (160) Vans Ne a Zao EC aa AY reetve eimination (coordination by alkene) S H-migration TEEN (186) 2 TEEN 2, alkene ede insertion) va (182) (alkyl-nydrido complex) Nacsa) Scheme 10,13.3.1 Catalytic cycle in hydrogenation of alkene by Wilkinson's catalyst, (Rh'CI(L)s] (L = Ph?) © scanned with OKEN Scanner> Reaction corinate Fig, 10.133. tastation of kintaly contol stesonpecifity whee the minor omer racy a 10.13.4 Hydroformylation Reaction (Oxo-Process) A. General features of the reaction Hydroformylation reaction: In this reaction, an alkene reacts with CO and H, to = : In tis reaction, an alkene reacts wit Is '0 produce hhaving one more C-atom than in the starting alkene. ‘oaleng R—cHOH, RCH CH, +H, + Co-2Be ACH OH # og, a ¢™ ‘Thus apparently, Hy and CO are added across the double bond to give the aldehyde, The tr hydroformylation arises by the consideration of addition of formaldehyde (HCHO) acros ie double bond leading to an extension of the C-chain by one unit, The introduction ofan On generates an active functional group. Bot in terms of the reaction mechanism, the process is noi so straight forward and he mgs misnomer. In act in terms of the reaction mechanism, the process shoud be beter deel! © scanned with OKEN Scanneri Cragtaan, } amounts ofthe straight and branched-chain pase sat ee rots depend te ranch hadnt pr se nn le ih hn pd ces Meseageile set Wr ne importance: The altos rhe atin eed pm pant to manufatr the erga iy comer in cbt wich isos a lasicers eg 2et ee rl ion nf hy a al ex) aan eS nechanistic steps of the proces in presence of C-atat (C400 ote as seen seca ag esas 25 HO aD el cx pe Fp {CM al gration ofthe ace cals Fo a reat i (SB tycoreOo an Ite specie) erred [co,(COls] +H: == afaco(co)] + equilibrium stained a igh pres) ic) (recess) Ciaran ft rr an a aes case CO. T preseason pi igh ps of CO. Ta oe oe een ee” eae ent ‘mains in equilibrium with {HCo(CO),)- [co(cou]-—= [Hex] i «) tue 0 / in be eat ‘This electron deficient species spas nee ovina eine 8 oD et tT ‘An optimum partial presu® ig abit meal a for subsemuet © CO coordi set (HCoACO THoaCOM very hi sssure ), generat epcition wil be dsl oe ‘(Coordination by olefin: O66" x "O)s] to generate an 18€ species: ale + RH OH Je Ts tis ee Heo(001). a © scanned with OKEN ScannerFAC CO cae et HB Oy Attn int the Com bond: 16 species and keep ‘wo isomeric (Le. branched and lin ara gop) con, ‘that hydride can migrate to any olefin carbon, To stabilise there (whe palpi ii) cst the 18e species, sing Fre tt he acess sy! cng: fom ony Tae mrad hte nde sigh cain copes we off addition of Co—H to the ‘coordinated alkene. - OP ger JK | [etre | forts osteo ee ain as isp a) (66 (5 7 [rewcr.co'co,| +20 = [roweros\co,] ce R R eo [o%e1—crco,] -00 [esr] an mich eo rar isrton of ne condi CO gro to ine he comple: Oe so {see G2 sepa ay compe migra he pion Bera tl por o {0 give the acy comple, colo, ] — > Festooy SiH co | 0 (1) Err) fl lent 0ic0), fe) RBI o4, Step 6 (Oxidative aon of H tothe 16 ay! complex gee 3 powcr, cab, (c0) ean A ieee 8, © scanned with OKEN ScannerFHF colt. (C0), s] [rc — | (-dhyaconin ta cH, 0 n of aldehyde and Fegeneration of the active catalyst): ° cH,Che — Pees] —tretc04) + RCH,CH,— of ow 4 ° I—>[He0(co),} 5 Reno 4 ROH —F—CoMH)(CO), 1 ioe re tHICo(CO)] may participate in nvo cen Note: with ol ire reductive elimination process to give the product cursor, [Co,(CO).] as follows lyst precursor, and catal os Teme +o RoHicH,—G— colo), ° (tenconpen) (66) 9 se ° [Heo(Co),] + lea G-colco, Patan c x i [co,(co),} p ° © scanned with OKEN ScannerDae Veswnahne NPs tan at gn td tld 5 Rese) peal] Reeve SMa cota, Reape —& 4 7 Bite sete —wytefermyttion , sneer, | 3 Mindat rttgunrmtonih as, Bear. He & Wate pen =e gan) ioe , ey ra tinea Slaps) Generation { uctve Cantal ee [i tow cto? wm alrtogts] fertoes vs 2 Ih toca] Sapo H (erg ™ cll. © scanned with OKEN Scannerep > * panne © scanned with OKEN Scanner© scanned with OKEN Scanner10.13.5 Monsanto Acetic Acid Synthesis Acetic acid is required to synthesise many industrial products like cellulose acetate, acetate este mainly used as solvents, vinyl acetate, pesticides, etc. Dilute acetic acid solutions can be prepared by bacterial aerobic oxidation of ethanol solution. Buy: in this process, concentrated acetic acid cannot be prepared. The commercial process (called Monsanto process, developed by Monsanto Company) is the Rh-catalysed carbonylation of methanol. Rh CH,OH + CO—fgpeSoagamy ? CHCO2H In this process, all other Gr. 9 metals i.e. Co, Ir’can also catalyse but Rh catalyses the process best. © scanned with OKEN Scanneror i : @ RhCl; 3H,0—_oo., i = 8 ndton faa an ‘al Con, ROO), + ing material CHOH i, st esting me HO ag piel Snthesis re CO42H ee, Ne ie Satie CH,OH qos #80 aly bined fay he ous) Hf 8 mixture of methane and ony 8 aes ua oxygen (9 octane ie a under & pressure of abou : ica efron se ey np im ae 4702 Same CH OH anechaiste steps ofthe cata cye 1 (rds; oxidative addition o CH, we Speci ally eroded fom Rh itp ena RMCON We pc Ie Ie seses of ROOD Cie. dyn) ideal expen sagen Teco i. om rmcoyyie| Sw | 1m |, io] eee AN, : (000.0N.5 ‘Step 2 (Migratory insertion ofthe CO group into the RhC bond): One of he coined CO rou is inserted into the RCH bon fo ive an acetyl complex, a 1e species. i ive 7 |Noo] ] heir plex): CO group ey tn a ein iene nme (mreoteouy]: Coren Ee (06 creat te © scanned with OKEN Scanner‘1622 Ri 2 em Nis Nee Dn00| + co —=] Snr ie | “Neo (1 ‘ Step 4 (Reductive elimination of acetyl iodide and regeneration of the aetive. catalyst P| Mog |e Ny Z| Se | : aN ain ma oy (Acve catalyst Asctyloie on yogis pros act i nd yo acid which canbe se ope ‘methyl iodide, aa Or — 61 i soHCOMH ol ° HOH + os - Ho Role of Fas a catalyst: I (ce iodide) is essential as cocatalyst in tis rocess, No ober sna inlaing the the aes ca perform the task. This uniqueness fr I- artes fom he oe factors [RAXACOLT (X= Cl Bs more reluctant to undergo oidatve ation becuse ier elecrnegaity of CB nat, [RAX,{CO)yisa complex wher CO acts as th ign and higher electronegativy of X will dexabilise this CO addut (i) Oxidative addition of CH to {RHC the rate determing step. Among the die methyl halides (CH, his oxidative addon steps kinetclly mot favour er C1 reactivity order: Cii-=1) CH—Br) CHCl) CH, Gi) Forte soft RD eee, Beng icy sot san ideal gan. (iv) The acid steigth sequence HI) HBr) HC indicates tat regeneration of mei ald fet ‘methanol is most favoured for HI. CHON + HI CH—1+ 4,0 In fact, thsi «hey reaction forthe over sucess of the proces, Fo the other weer is le HCI, HBX, the process sno so favoured. © scanned with OKEN Scanner