SYNTHESIS, CHARACTERIZATION AND CATALYTIC ACTWTTY OF TRANSITION METALS COMPLEXES A dissertation submitted to the Depart Dent of Ch€mistry, Quaid-i-Azam University, Isldnabad, in partial tulfi llment ofthe requircment6 for the de$e€ of Doctor ofPhilosophy InoryenidADdyticrl Chemistry by Malihq Asma D@altmcot ofcbenistry quaid-i-A.ann UdveEity hla@bad z0LO
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SYNTHESIS, CHARACTERIZATION AND CATALYTICACTWTTY OF TRANSITION METALS COMPLEXES
A dissertation submitted to the Depart Dent of Ch€mistry,
Quaid-i-Azam University, Isldnabad, in partial tulfi llmentofthe requircment6 for the de$e€ of
Doctor ofPhilosophy
InoryenidADdyticrl Chemistry
by
Malihq Asma
D@altmcot ofcbenistryquaid-i-A.ann UdveEity
hla@bad
z0LO
DECI IAT|OIIT1'! s b dit rh.r rhi d.dM qrnbd "ryr,.d,i c aM4bl' .rd
ctuIr^k lddo ot TnB!d., atub c.4r@" ia.nift.d by rri ,' drr,ah E Ecrr.dr r p@' rofl by 'll D.p.nMr of chdlty. (\!i<ri-^m un,vsjry, titnri|d.P.ritu, E srirtins dr ldrm rcqumar ro h. &sd or D,6, d/ Pr{.,qrry in4,d'd..n'',,'d. aEe'4
polynsia e$ylae lDmo8hoully !s w.ll rs to @polF.riz. it wiln olha oLnrs
l.l Typ.s of Tntrsiairtr Mctil Cradlnt!Ixe tr|tl|]oru abt$ rrotrn rrod.y c.o tc cLsif€d Mdirs b EiE
ciiE n: $'de, @rp6itioo, !r!. of +plicdid d nd. of.gecgditn Tld! @ tsIsge grq4c h.rdogaea c.r.ltrr (5lit rd. .slyrr) ..d toD€@rB drb,$.TIElGd$gEi tu da ft.B ar6.r hoogmB cdt*.qd.d to $li6(rpo.t d cddr*) de rrom G iml|obili*d.dtG
In rulDoncd er.lysa lte cdrylicdt &tiE 3ut i.@ ir.pdi.d lo. $pDorr @ridltdh.rhrgc,!6e.E&d!oudlyF(ouBytrlt DodioF.ild.$lrischcrelgaFB cdlFri tiomgqFuly odlyzod r!..,lioG c codolhd ditrty by
tirctios .nd les by D.t rirl t6!rpor! b6|u!. difrlio. ofthe r@tad to rhe cdJyrtcrt ocsrr ndE npidy lrl.
Cbd l.t fbw.bn ofclllificiioo ofc.lrlyr3
N@r"al Ni@) . rl/!a of tyF ts{PlbPqH.(co)oNi(rhxl) ui.e si.tlHitid O.fin Po6 6HOP) F.6 LF 06r r!.d to FldE l&lly li|E dyiiaoligoGs. wta LtiL .p..rro. tis.d. sb a ptridiE d !to.?ruE rlid6 &uliliz.4 D.dir6ed SHOP oLb6i Fod@ bign m|edr wighl lilE pot*rrytc I'n-
&!o&tdtt golp slu rd ttn hlty ryl iEiG c E$rirld f6 dr F{.bdio ofnigh
ettc ld tolymrizrto. of dhyLE io F.du@ lind Flv.lbvl4 041tu ndcutrrcigh i. nodotcly high. wit! l/"- l7od, ltnolr, whic! L hi hd llD ll*DolyclhyLE ptod@ld tt M} h l[i. @ s oliSpddic pt dsr. s@ oblrb.d.
u".e'"t*I'
ryrl tvrl
l3 Notr-Cp B.s€d Crtdystsr3.l Nl-chdrtcd C.tdy3r8
Itu &EbFE or ti6ly rctiE Ni(tr) ud PdCD bs.d qdt$ 6r
lll. scmltyp. (AtN.qRlqr.FN r)M(Cft)l fo. Poltndi4!@ [email protected] i! eu &cnard. Tn t*ri6 of [Pd(M.CN).1(EF.D ttd
A.N<M.)C(MGFN (A!-2,rc.Ht-ih) lidq 100 Dti of .tnvL* pldG irchldofon EolEd hi$ly @rpholr loVdnyhF. Tn PotDd oonircd i. htltv
bn ch.d dd .h. bnehiiS lod !t!d dilEibuio E id.nticll lo lho& obtri*d sh"
thc wclli.6n.d initilor MU] b u..d s qulF
| _-Fll"(). II -*'l
NrtrI
Hilhly bEcb.d polrDd D fd!*d dE 16 Fbv&egd cliDiuliod/ Gintnid*ti@ wnh Frgdnc qtidic drtl i' dEdn& !pci6 lr c@Plax l\qll.ryl nt8,
ln p6p.!dicd.r io th. iqre ptu SorEtry of tlE cdpld sd i'Pr 6oi.tv .1dr
onlb D..itio- fiii rbdld F$n s. Ucrrg. of th. Djd .Ptro.cn of oLfc lr'h.ntrs6 dE EL of ch.in [email protected]. s onFEd lo tl& nE of chdn t afar !'dEsull. in dE fom.lion of . hi& nol4lLr w.i8ht polvffi v.n@ qlimi Ni (lD
conpld.s b.,cd ot uthindald d-diini$liS!& h* bca tt$aiz.d Dd Fov.d ahighly tsriEor,ly.t fd th. oli!@i4tior of .drk c.
tD(l
Ixl tloigsin MMAO ?5t.rlibils u.t?.6t o!:rog tlqufiv of 94IIoiTO hi. ft* bShly.ctirc Ni (IDqrrlyit N D..d for l[. lap.nrid ofcd.6N
Errjng n@ Ca{26, wilh *l€rctivity of liE ddtfis s high s 9a% Er'
Gib.or ud otorlcn n w Gtdr.d . ed.. of [email protected] !dt!ti.dch@iu (Itr) qol/rL dLilbs B4-r.doE 6 /rmlittFidiE ltEd. for
otir.|Eizrrid .!d tot uiad@ of crtd. Pr. Th.$ lis.n& id fi6dn bow of
conDld* and dEn c.brydc &dvjty fd oligondiatio of.rhvl@lal
1.3.4 P-N-P chelct.d cddysl!
various chromiun cdplex.! wilh P_N-P liglrion lBv' b€en u&d as cfiicienl
c&lyc fd ll'. $l€1iE ceriD.rizltion of .$cm ind porvftn'non or stvlw t' 'nctrlhcyolic mecheiln lr.doniDetlv, lincd Eetcrirls art obtoircd for 0E ftthoxv
$bltilnL<l ligmd. Ey v.ryi4 ih. tig$d sauctuF, d' plldtr'rid dislibudo cN b'
and DoaIV-bl wnich conbib tne morc weatly cm'niMtjns lnions [BM'(C6F t and
IB(CtrrIl , ircl€dd with iim. wbm. tnN Doduccd bv [)(,\rva] (CFrSOrl mit.de$.ntially .onsbnt with tin.. In addilio! i. ti. iMrd& in solccurar w.i8ht wilh rinc'
*iih n rtllo@e @mpl.F of Ti, Zr or Hf (cidd sutslitlEd mdl@d or lh.n rins
subs.itucd @loerq), ficy fod ehltrictlly tdiv. svs|.ms fot th. potvhsiaton of
.thvlcn. and d-olefins. Howdcr, wh.n MrBul and AlElrCl wcE u&d llone io rctrvale
fi. zirconaeE @nplcr, Eids M!Bn, nor AlEtrcl w!. .ffet d ttr 6e ol clhvld'
rcDolld.rizlioD c.ciiom. polyhd yields nts.d ft@ 2JOO ro I0,OOO g mol I of Z!
conD.riso! wirh MAO s ! oo-clElyd sho*cd lhrt Al&Cl_Ms& coobinatios *q' 5_
The Al&Cl-MgR! combinrtims can ako acrivtt bndM md.nomc conpld4 in ihc
[email protected] Dolyn.nation of Hl.ns Polynqiatio! ofpFpvt'n' vnn &dvai€d
C,HaOnd)ZrcL by ^lEnO-MsBlr
s @.rb$r w'dl ii [al]:tMgl nolrr Etio of 2'3 it
17
50 'C rnd propyl.n. psnill pEsE of O 48 MP. prcduccd Polv?opvld. (2 h vield -200 grnol ra) wirh a n.d.EE &!Ec of ilo@ttcitr iG n.lring poinr i5 136140 'Cl*1. Trinuclar ?d-diinirc lil sd id.uclar DAlladiln ritidbsn hrv. h€n Gpotud ro
prodlc. high nol.crlar w.igtu lind! rblyeth/.rc Fr).
1.8 Copolymenzatiotr of Ethyl€ne with V.rious PolrrMonomers using Transition Metal Crtalysts
Th. iDcorDoniion olpolt gDuls i o r polyoLfn c[ai. innn@t Dattv icv p']vtdpropenics, including ellctt r.sisl!t*, surfac. prcp€tlic! (lainl abilitv, pnDbbiliry dc )
b'ri4 p6pcrli.s, grs p.@bility, !dh6io, nmdbililv, toughnd ind rhmtl
bariei. An imDon Dt fet$r oI succ.sftl c@olvnenadon of polar nonond qnh
.rhylm s r rb'l'ty ro @rFl rh. .no t .nd dbhbunon ol rhc @monon?r In fi'Pl.dud. Anothd inpMl d.teminbr is th. Elitiw r4tivitv of lh. Dotoocs This
depend! on th. otbiLl eturgcs oflha Donm6 ud dEir &srecdvc inteEct'lc d4i'swiih rrr ftdticr orbital of dE ciult€ls. A monon( with a@d overlrp of orbitd
cn.rsica viil th. cllalysl vitl bc ihc prclmd subttalc in polvn.nddon lrtl
B@l(n,n Epon d inpon&t ratuE! d.cdiue the raihil'tv ol
coDolymcliation ol ethylcnc wiih difi.rcni conononqs l@l
l. Thc Elrdw biDdirg sbglh of cdryl4 rnd GrclMs2. The rclalivc itu nim Bte of.lhylcrc and co_momno
3. Thc nG of.lhrd. iMnion inlo neli{t'hon bond
4. Fc.sibility ofclEht loftcrion lner .$vl@e in*nior and oD€ting ofchelar'
Ir 2002. Dr..t Epon n n ult l P, Ol Pd cablvsls 10 @tolvbetnt dhae 8nd
smc i .cnif,a E$lE h.v. len obri&d usins PllhdiuD 6npl€r.s fdclrloDolyll)dizrion and coDolym.nziior of a md o ditus wirh .thylcrc ltrl sinilirly,
lor copolynonation ofcthyl.no vith CO lt:),
1.9 Aims and Objectivssn. following .r!eB w@ .h. ri4 of thn $.sis:
I To rydh*ie !.w tusition mbl clrily* contlinin8 td md Cr ELk, Firetuhing of th. smcturcs and applicllids in oletu polyh.nanon E&hom sbolld
Foduce D.lyneri wiln @ntolled dehei€l pbp.rti.s
To sbdy sdftrdvi9 rcbrioGliF of rtc d 6cl!l conDlds !! oi.ts!prrrnng $ihblc c.Llysls vi$ ,or.niirlly hth c.bltric lcrivtties.
To study tnc rdclion n.chdisms i,volled in lnc poductioD ofpoly.dylorc and
copdFe6 ofctiyl.n md various pohr nmm.6.
2.
4. To investigai€ rh. .trel of nir.d ligmds in rd .ompldcs d it!. .ihylmoligomenarioD b.nlvid op€dns up i n * disou$iotr oD li$nd erivity.
5. To invdi8lc thc copolynqiation b.hrvid oI [P,O] p.llidiun @mpld.d ror
vlnos P6ld tuMc6 sp€i6-lly rllyt .l!yl edE lnd .llyl bDnidc.
1.10 Future OutlooksLLDPE is pbjecEd to ftnain th. lb!.!l srcwing polyolc,in with oonsumptid
dolblin8 lioD tE y@ 2006 (l? liuion tgrar) b 2020 (34 ttlion k8/yd) ,sdinrLd .nd .xprdi@ Iim lTyo b 196 oI rh. Flyolcin M].er. llE loltndnlnutrctunns G chhaing EFdly in ri.& d.ys. Ncw d.wl@n* rs in lolyndindusEi* is drivd by follovins fcaturd such $ slns.sis of n.w cctalysis, d.5ign and
poduclioD of rew polymcE with impbv.d lnd cortollcd Foprnies (ndible, m@
st@gd, hish LnpcntuE Birblr D.cdds), dewloprlcnr of ra polyn darion
n.lnods Prr. L vid of O. obsF.d pogE$ in rb. Dolynaiatioo ficld w h!v?
plann.d io inv€stigib otha ts$sinon D.trl conpldcs cdr.inin8 N, O md N, P donor
.M d d.n u. fr. b t!.b.d@ ort4'@ Ed ..?orynd d.dol6 ribdit&(!d 6no|1.ffi F.|.rdtg di&6t chdoLtidict lo dlci tt tEloi&ndd.{rlt ! low cod, Fli.liltt , nfddsilili.t fo.ilihy.!d ltaDd llill.d.18v.tor.m!ri.&.urtodboliotaras&dbudidllidF64
REFERENCES
I
2
!
hel, s D.;John$n, L. K.iBrmkhin, M. Crs, xzv.2000, Jrr,l169.
Tm Didlqtl.j Svoboda M.j cri.^a,r-Z.Natu4or6h t r,36b,3!2.
vd Aslt, R; El*vicr: C. l.; SD..r!, w L Li Sp.k, A, L.; Bdcdix, R, Rcel
Izv Cri-, Ply$B6 1994, ././3, 38.
vai Kord, G i vrica, K Adv Oganoka Chn.1942, 21, 151.
Wcir6crg, W ; McF dand, l; Goldw, l.; BoD$i., T. R.; Couerd, C.i
Tuner, H.l Mu.!hy, V.Pow6, f. S. AnEN Ch@,, !nt Ed. E CI l9a.37(23).3212.
6. weinh€rg, w.; McFrldd, E.t coldqr$er, 1.t Boussie, T iTuma,H i van B€*,J. A. M.j Murphy, V i Po*€n, T WO Pib Applicnion 9803521 ro Synla.prionly d'l.ruly23, 1996,a.dU.S. PrcDr6030Ut, Fcb 29, 2000.
t2.
10.
Br&a,6.; tucci,C,iShma c.iciu,ri, A.; cdgli.lnjoi B.; Glllctii, A. M. R. U.
Durchis?d iom Albctule 6 1.4 M elutim in lolue* Modi6.d n.thylduhinor*(MMAO) I 9l M in lEp6. ws puEh.*d frm Ar- CoD Die0ryllbninjDn ctldi&(Et:AlCl) rnd ethyl iluminium dichlorid. (ElAlclr) *.8 pu&hs.d tom Acbs and
Alddch ch.nicals. All otbq cidicals includirg 2,6_dicirbdnoryrridi* w@
@td.d by EGEM io dE Esid!.l elvdt siea.ls lolv.tbvld. w$ chectnz.d bv
rC-NMR sldtueopy ud sisnDens w.ft confimed bv DIPT', 15
2.2 Procedure for Oligomerlzatlon and Polymerization it 1.0
etm Ethylene Pressure
A Di.n.i.d Fi$hcr Ptu bord. .quiDFd *irh i nlgn tjc bli w chrg'd with
lhe ct$ly$ (20 lrnol; 0.012 g) !lo's wirh 50nL of blu.tu in r slov€ bd ft wrr
a*ombl.d ind artuh.d lo tne etfiyl* slpply line d.d h.rtod ilon8 with mnsllnt
stifin8 for 15-20 nin to F.l€ suE thal d. cit ltd wN cdplcr.lv dissolved Th.
rcEtion nirtle vs nirr.d fd 2 rr ar 30 t &d 50 Fi edtld. pr.$@ Lq n {sc@lcd dom dd dE soNal w6 dlPoEcd Mdnel e0 Dr) ,$ .dd.d io Duip'nEpob4nc. Th. polymd obLir.d *as
'ssi.d *iln D.rbdol (15 nL) rnd chloFfm (l 5
dL) The obuined polyD.r wa3 dricd und.r ucuun oldrgni
Hirn FsG olirpddir.lon -d t lrEizlrid rsiG r* 6i'd od in r2tO mL slllnts src.l.urel.rc ftto.€quitt d *illl n*hsid niEr ed th@os-
Thc a.lq ss dri.n in d own Fior b ah M.nd Frged *ith N/ luu 6eritd TIF cdlF $lotid ir tol4a (30 nLI d. @trlt!...i1tiicE @ 6L) E!rdlcd io rL Ed. undcr clhvl@ lldd.q wnd dE Eq!i'!d lqlpdlE sr4h.{t .ihykfr .r &sirql pt!.@ o0 dr) 16 iftlduc.d lo tbn Edha lLEdm s n rp.d rna lonln by tdli.tiig dE .ihvlo. stplv b th' 14Lr
v*t. A rddl @ur of lhc @lio $l'rid E olLd.d bv . lvriis. lo N$4 dE
olig@dii&tn tn qErd tt rldt J X ad! Ucr il'rir Th' |Ui'itr!slori@ vG r.dinar.d by ldding u HCI .ihnol (t %) elutid TlF polvtur fmtdG fdtec4 slt d w n dhltol, d.in uia t&ud d 60 'C to .Nl.nt wEhl
ftirH d fdly c[&.tqit d.
JO
iElR tlr Pe-Rceior T..nniqu. fq High Pesua R€did3
Dilt Ml tyF! of chrcmium sd p.ll.diln cddyrl! wE pEpdrd lo invetirnclh.[ eldyiic ..rivi9 tor oliS@ianid .nrl polynqiztid of drlyrcm .r wid3cd'ylft pcgc- Ptll.diln c.tdtst w.lb cmplot.d ro.ipl@ c.polynsiziidofa$ylene wlth pold .6monon.R like rl0l .thyl .lhd ed allyl bbmid..
sydndic pre.d@r of th6 ohMi@ ..d Flladim clr,|yns ed thcir
chad.tsrizrioi by vdious sp€Lo&opic tainiquas e rJ follo$.
2.{ C'hroDium CompleresTh. CFconpl.x6 C-l !o c-7 w.rc synrh.siad in epod yi.ld by rcEling CCh.(IHF)r
whh llE @Gpondina ffquircrrlic2-yl)prridinc2-rDdnrfi&n.)b.@ miR in
dichloron.lhn . Th.ir r.suldng sohions ww ooi@itdtcd and diethyl .rh6 ers
.ddcd ro p@lpirir. olt thc !rcd@t3 t'L
0.182 hnol (0.0639 g) of quimrlinyl-imiioplddi* (Ll) ws .dded 0,182 nnol,(0.(X3 d C|CLGHFL. th. elorid v6 riftd rq 2,i h .t @s LmFnie sivi.s.i4 gen s$!.Nioi. 'ft. Bclion toludc w r.duced by .v.todting !id.r vacuum.
Dicrhyl d'.r *c ldt d ed s n $lid w.! oh&ined. TIE dlling pcipiEtes 9sw$hcd rwic. with di.thyl ethd lnd dri.d under ucuuh, Tnc tnal @mpler Ms
I
obbiRi c grn to{da vhicb G crysolian by slor diltusid of lh. $lulion of lh.
conpl.r in didnyl .lhd itrlo ! h.x.Dc layall.
2,4.1 SyDrh€sh of 2,ftim€thyl-N{l{6-(qulooI!litr-3-vDPvridim-2"v1)-.lhylideft)b.@tridlacrcl, IC-l]ftc Cl contl.x *a. tFthcsi&d by dE saN poc.dw a d.sdb.d abo€ 2
and Crclr Gls)r (0,24 nmol, O.O?9 s) Nefr Escled b fm 0 165 mol (0 039s) of a
sF @nprax wirlr ?3.1% yi.ld. lR ' Dd (I(3r, d_r) 2966' 1589 (v Gl'D' 1485'
14t4. 1371. 1115, 1284, 1159, 1129, 1095, 973, 351, 78l C.lc for CtHr.CBCrNa: C
55.7, H 4.5. N I0.4, Found: C 55.4, H 4.3,N l0 l
(C-l !o ctl
[c l] Ic-2] lc.3l tc'41 tc-51 lc-61 [cr]
RI El CI
H H H H H H
Sc!.b. 2.1: SyDlncsis of ctuomiDm cdtldcs [Cl !o C-7]
2.4.3 Syrthesh of 2'tdltioPropylN-(r-(6(q!iDoxalin'3_vl)Pvndin-2_yl)ethylld.re)ben@i"€.crcl3 lc-31An amlogod precdlE s lpplied fd [cl] w.dop&d to s]ntha.i4 {C'!l'
Sohtion of 2,6niiouo!y!N-(l-(6-(quitoxdin-3'vl) pltidin+2_vl) .lhvlidetc)
b.Mruhin. IL-ll (0.29 hnol, O l2l g) dd CtCIr GHF)r {0.29 mnol' 0 095 3) in
dichloron.$.n. weE slin€d fd 24h Eslting a s€cn poNd€! iD 65 7ol. vteld v nix
(xsr,.ml296r, 1584 (v C-D, las9. 1362, llll, 10s9,829, ?58 Colc for
C,HTCDCTNa: C 572, tI5 0,N9 9. Found: C s7.6,H4 6' N l0.r'
2.4.4 Synthesl. of 2,4,CtriE.tbyl_N{r-(qquimnli!-3-vl)pvridiD'2-yl).ihylid€tr€)benzlrimirc.crcL [c-41
A 23,6-tis.lhyl-N(116_(quinoxtlir_3_vD pvndin-2_vl) erhvliden')
beMnDie Gal (0.25? nnol, o O9a3 d $tutio € .dded ro CClr OHF! (0 025?
nmol, 0.0323 g) in di.hloron thrn. A ligh gtd compld *a3 oblained rit'r 24 h
sriring { r6n t DFibr.. A sEn }owdd in 60.2% vlcld v ftu (KBr, cn ') 2959.
PdCh(CHf|0: {1.29 g, 5 nmoD w6 dn$Md in dn d r@bE (20 d'l-) in ISchlok tub. und.r ritog.n. A $lution of Eph.Dybnos?hie (l 3l s, 5 htul) qr!dd.d dopwi$ b rh. ldCL (cH:cl9: iolurion, Th. ErclioD nixruE w.i Enux.d fo.
o.5h lloDs will: cotubnr stitrin8, A lidir yctlow pMipit L w4 oblin d, Thc p@ipitrt
wls iltcr.d and m$.d twic. wilh dri.d EloH. It. !@nd tup d cqurvrldt rnouDl
oi N-m.thyhnilirc (0.5! & 5 d6ol) w$ !dd.d dbpwis. lo a
tPdcl,(CHTgN)(riphdylphosthi*)l susFision iD cHzcl, and Enuxcd foi I h A ddonnsc slutior w!! obtain.d. A cr'€lallin Foducr ms obbircd stut slow *.Porotifl
2.ll Characterlzrtion of poly€thylene .nd co-polymerg
All chrcDiun cmplexes qc.Dl 2,tuinuoGN-(116{q!indlin-3_yl)€$yl-
idflc)b€[email protected]! (C5) Foduc.d lilnifE$r quftiiiB orpolynG Thc polyndobbin n *E chmtnz.d by IR sins Xlr di$ tt rh. Engc of aOO(H0O cm r' Th*Dolyn s !E linor .onfmcd by ch@Hilric lb$rDdd brnds of C - C hd C-ll.
Diffdmtial Scamins cdorim.try (DSC) lmlysis of .ll polF.ts tra elscondul€d on a P*kin-Elnd DSC @lorincld which illuttald lhll thc nclting point
6ng. is l2?oc b l35oc wi6 aagi6 b.N*i llclT? Jg . Tho Erction t nDqa@
h6 als . sut irLt!@. on Tn rc) of PE. 'nE @tion hDaN i,c@ !l$d.c€.c Tn. flE* qles e @situr ,in $a r.lucs obtain d ld Hid densrq
Thc sl. ofbis(iDino)pyridine od noDo(inino)pyridirc d*ivdivcs cs tislnd! iicompldes oul aE us.d for €dyric .dryl€oe Dol)ftliatid en nor b€ or.t.nphasizd. Folloyins lhc ind.FEndc di$ov..y or 2, 6 bn(imiDohridrt ncrd G.and Co) @mpLx.!, F sucn €bvsts by Br@knrn and ciblon opcncd Lt. dor ro hiBh
d.Niiy po\€thylcnc or llplE olcnns. l,{. M@ovs, rft6 rh. piolM wo* orajiimiDoni.k l 6npls.s s aLlysl! ld dlyto* pobndizlrion 0, idji6p"idir. nicr(.r
conplcres lrqrrrind $.i' dibdic.nlogu6 I'ir werc folnd b b. lctiv. c6t tFs fo!.ihyloe polyn.dation. Worlh to be maliorcd dE prDladon ofth.e inino-pyndin.
risrDd! omoDly inrclv.s rhc us of @qt. or fomy! plridin .s snirg nlt ri.r. To.lploE the alr.n.rive nod.k of laL-r.nsition n.6l cfrplqe a5 rh. @lalysrs to!crhylde p.lyncriation lr: rl 2{nb.dDxy-6-i€tytprridin (5) w$ tusl pEDlrcd
thbugh ill. cmdouabL Fefomtid of Don€arb.rytAt jrlo an letyt golD with
hand .vid.nc€s for uDd.Br.ndins then phusiblc raction h.chlni!tu. Ii.ft, rh. dcLiil
ftsulrs lre r.pon d alo.g with dE di$u$jon of tljc pltusibl. hah.nisn.
In dE f@tior of 6{c.iyl2ert dFrrlyidirc (t lrd z,tui.arytpFjdiic(9) noD 2, 6-{tic.tb.thoxyptridirc (t), n i. cld thr rh. Chis 6ter corddsltionbkc! pltoo fmins th. coftsp.Ddins rn.loSrca of 9-Lelo csrd I,01. Then th. foltowirs
hydolysiB in acidic rqu6B slutio will hTp.D ed cl.rv. th. u.b€rhoxy group wirh
thc n@6ity of eicErd F:.rion r.np.EoE. IrE inpodnr ise Ellrad b th.cdr4ion ,icld vill invols rhc.treii!. foturior ofdicrhoxy{ropopdol.r. (2 or6), rhich th.r p1bducs rh. Fkclo esr.r lDioDs (3 or 7) nEle sggolcd lnioDic
conDounds corld nor b. diEdy obEincd at fiis momflt fiow.vd,ln. i.ohbd p-t.io
e..! cohportuls (4 or 8) 6uld Plovc ln. pED@ of Frdo .!o.r si@ (3 ot , 'r
rh.
b4n $lution. Tb. Ft io 6h @DouftI! (a or 8) ieht d 6!ld rbvi'b dnerelid.nccs i. fonirg ao.ryhhc conpouds.
59
tn dr. c{ book of orgsic cbmisq, n is cmmon b sho* dut 6. fo'mrion
of an acetyl ssup Ird . p-t.b .*s con occur in 5 hydolvzing irs 6t r grouD lo fom
rhc 0 kcrd rid m an intemcdittc i1 vd t hy?orh.sis [email protected] in a prdious publication
&diun .rhanod. *3 connonry p.Aed . d.icd ton il! admol soluli6. Hwwd,some elbinol could rcmain in thl solid NaOEt, .ven *hcr il t6 dned und41,cNm
line Mo@v.', $diun hydbxide @uld .l$ bc .n inpuriry conpolnd du. to ih. linle
lmur ot v.t r lminils i! 4bmol u$n. IE* fictoE viu lfat tt sl hou't 6r
NaOEt, lh.EfoE il is na${y ro uc an dc.siv. dNr of NroB rr': L I I e} lor the
rdnsfomrtion elctiotr. Ll6.iD, irstad oi ugins NaOE! tnc sloicnion.Eic e!.dor of
clhml ud $du itr lolu.na Dovidd fi6h N.OEI in cf-riv.ly actiutin3 d. Cl.is.dd cdddsiion. wid' thc $n; volk-up prcc.ss, botn deiEd pbducr!, 6{evl-2-carbefioxrTyndinc (s) md 2, 6-diacdyl'D{idi,. (9), wd oblajned wnh hislly
inproved iclds. The 2-s6.doxy-6-accrylprridir. {s) could b. Flp.Ed in 6l%
ielaEd yi.k wnh m .quisldt of sodiM Ed.rb.sl itubd of45 % tidd {rrl.
M.m*hiL, 2.6ni&.tylp"idiE (9) b ,.Daed in 66.1% yi.ld wirh 1.0 .quivaldls
of ediun dd ctheol conplr.d with rh. ln*atu€ yicld of 58.8% rrr, Bcyond r.b! lnis
preeduE nede l.$ oolnts of subsbnc.s l.$ iib. and .n.8/ In lhc rbchion.ticlmunt of sodtun, .rhlrol .nd 2, [email protected] 0), a tuc of 2, 6niie9lpridin. (9) was obsefl.d iD .dditior lo 2{.tb.rhoxy-6nc.tylp}ddin (t r.ct to tne
fomaiio! of @dbhion ccrboxylic 6Lr. lhc n$ction of NIOEI is ro Enov. hydride
will diedt produc€ son. B-k.to .rGr. To rloid c$lnol foft.d in th. r*ciion, .hc
toluene b u&d !s solvcDl *ith sood solubilitr ol2, 6nic.$.lhox)"yridift (l) ddpodlcll. with firilg domr 5 .quivdolr of .oryl {d.e b 2,&icar!.thd}?ridiF,
rh. roft.tion of Gac.tl-2{.d€$oxrTyridinc (t or 2,6ni.@tylpFdif,. (9) was
irdividully imprcv.d thelgh co .ollins rh. rnomis of sdim. Th. 2+!Ibcrhoty-6-
.€rylplidin. wis elely [email protected] in 67.1% isolaLd yi.ld with onc .quivalht oisodiln, qhrl. 2,5-dietylDyndine 6 i$lltcd rs rh. dly Droducr iI 7l .0% yicld wih
Unnl now, thc anouft of difieEht r.aclanE h!v. bcdr tully ddsideEd lor
fomadd 6-acciyl'2{srb.rtorr?yndie (5) or 2,6-dnetylprridinc (9). Th.Ef@,
Efrio n€hDtm shdld h. Evis.d .s d*db€d !bov.:
ln lh. r@tions ro fon rwo peducts 5 dd 9, the Dsr.bt. dietnoxy-
oxopopanol!1. (2 or o aDd p.t 10 6Gt dio6 (! or t) would be in&m.dirt s. Ethyl
.c.rir. @cb wnh sodiui lo fh ! 6'brio, cfborylic 6Lr, whiD old n pwi&
Ead wnh tuo c.rbelhoxy 8rcups ot 2, 6-dic.rnclhoxwyndinc (r). Th. pEenc. ofN!OEt could som.how Esult in rn unbiluccd Eoclion lo fom nixrr8 ofNo DFduct!virh 2, tuicrrbdtb4/p,"idim (r) !€rui.iDs. Hovdar, lodid i! nor dn&lwd itloludn Md rcact5 st gwie wnn 2,tuidrb.lhoopridi@ O) in rwo 5Ea.r d thc ba*or th. sodiDn lbounls. Ndnaliaion wnh diluhd HCI in ic./watcr blth i.pEs6, ih.
'ntrnedi{cs of Fkcb @boxyl.E 4 ad 5 wE idrividuly ep€sred jn
8ood yiet<ls Ileb in sffil .*cprcd tur rh. tydn!6i. of F+c!o d$.ryt&s sivci dE Fr.6c0borylic rids lr'r. Howaa, $d. is rc Fle oi 6-rc.rylpridiE.2{uboxyfic lcidobetudd in tlE hydrolysb of p-k ro olt6dylat s 4. SiDihrlt rheE ic ro rnitogucs
bc.n4 @boxrlic .cid i$I.t d in fomi.g dj.@rylpFjdirc (9) d'od rlc hydorysi. otdndyl 2,6-bis(F tdce$o:yhE)t'yddjm (8). rn addino", it ws repod.d rh,r lhc Fk.ro carboxylic acid was sbbl. erl. Tt Efore, n would b. bene! corljdenre an
.lcn.livc nahsisb. lnsta4 rhe ctav.g. rerj@ ot . Ft ro .sr rDtir.r thc a*rylSrdp .nd .thyl c.inoxyl{c, vhjcl t s un$bt. int mcdirE d,.t a b. ddilyd.conpoed inb.rh,nol md crt'oor djoxid. Ihh ph.n@cnon q.s also ob.cs.d in th.syrthdis oi l-chloD-2-.tkinon6 l,:1. Tno distty d@mpoling p-kelo o.rboxyric.srdiMmcly anti{lis! !@id, will poecd in tfic pEenc of pbiG ro gjv. e [email protected]
Stoup rnd.tlyt.dn ryl.rc. Iu)
3.3 Pall.dium Cohpleres Co
f, _,("."{ )f-I
lL11
Figur. 3.3: Prllidiun
ntrinitrg Mired Donor
lq' fn ^*lPfPdtNlU) |
tct | _:- |t-
lt2)
Lig.trds
All sFd.sizd prlladiun cospld.! EE chrncEnzed by NMR, IR !cl.n nbl odyeir !.d singlc cryst l X-ny Mlyris, The E$l!s confim.d th€
oi an N-H vibntim of dictlloh.xyldioo indioircd by a D.!k at 334? cDr In $e fre.PhrP noiely, . si8ni d l4?4 cD"r@|!gls . P-C vibntid shict iplar.d wid . rdshin .t 1465 cD-r .ft.r conpLndon @ffhjI8 dE ditiDlim of lhr! with pd 0I)n.bl. A band !l 16s7 coL Epr.$nr! thc vibstior ofphdyl gb!p5. Illc lbsoarioD
bmd! for Pd-Cl e h lhc nn8. of 30G332 cmn_ All !b&rpti@ vituca h.r. b.cn
r$i8r€d &@dinE to th. IiEntu Prr.
62
3.1.1.2 NMR-AnalyrisTh. rH-f,'l,,lR dr. (in CDCIr) for .mplcrs C-a ro Cl9 iddrifi.d lll prorors
by $.n inasity and muuiplicity pan.d dd rh. bbl numbs of potons was olcul.tcd
$a k r .tnifiot domfi.ld shiii i. dr.orplcxrs ir @npuisD b ln€ ttc ligdds
which cdtutu rhc [email protected] of thc ligrn& lirh D.d 6r.6. Th. dEPhrP noiery shows r nrlritl.t sigral ar 7,34 ppo Frwhich rfid mrdinrtion with
Pd(Il) cpp.5s in tne nngc of 7.3 8-7,?2 ppm h lccorda.dc lo rcponcd valu.s l:r:6r.
ft. mmtic poton siguls of lolylpno$nine rsorrD6 in the msc of 6 =
7.ll-?61 ppn aDd tlE 6 = 2.?8 ppn '!s.ne is orlrib{t d t. d. CHr noi.ry olrolylphospninc in th. c@9lcx6, TrE mrdi. prorc ol sbditut d dlir. aOp..r itfic nngo of6.9?-7.23 ppn whici iils wcll wiih litdtorc !alu*lal. In ln. cmplcxcs C-
8, Pd (dicyclohdylanincxLi$r-tolylphosthin.)Clr and Cll Pd(N,melhyhnilin.Xnie
pbtlph6phine)C1,, dE CHr noEq of sutcnod eitircs tetuB ar 3 08 .!d 5.J I
C-8 ro C-19. Tlrc 6MEr of Dhcghjn. .Dd eiiE rE lhind do'!6old in d..mplcx.s s compaFn b rhe lE ti$n<,r Thc arbon .lms in ihc ii&tiph.ryhhosphin. lig-d E;E ar 6 -t 28.4. 128.5, 133.6 .rd I34.2 ppn Es!-riv.tyPt ttr lnd ifEr oonpldrlid in lnc 68c 6 - l2?-l35ppn, Th. upfi.ld shitod C {-p)Eson.ncc in the Phf moicty is artribuicd ro I shift ot el@trDn d.mit nm tnc nc&l
'on io*tdr C (-P) dlc to th. r{c.€ptiDa DiE ofrbrt.
Amric C tlo anbotu or $htrituid anitinc Isnuc in d'c n.g. ot o - 126
129 lnd 135.05 ppn. In dE cooplq C-3, rh. cyctohdyl goup is .teron-do{tinA.'Inis would incEo* ihc dou6l. bond chldcrd of the C-N bond lDon cooidination
calsin8 a dehjeldhs of qrnoD atom !$chcd !o d. !cr.l cmt r. nE cdoB otcxroh.xylbic slDv ri8rL i, th€ nn8. a - 25-56 ppE. Th. mmdc c.tto6 in
lolylphoslhir. Esomt ir th. mgc 6 = 141132 ppn $ @nprcn b tne fe li8{dulu. 138-129 ppn l':x
':rl .Tlc C'lr- bojctb! of N-nelhyl.nilirc .nd tolylpho9hir.appqralS = 24.? rd 2l.5 ppn, ho*evcr, iD $. na IS.nd rh.y !pp@ !t o - lO.2 dd
6l
'tt pEm@ of thoc sollm.r clsily ndif6t d ln. @rdin.tid of hotr
bsli$fd inilino snd pholphine lisandE !ho!8l N- dd P- to lhe bclal 6nler' TlE
.M.lic E$|l.rc w@ &i8n d by @npbm or .xp.rimarr.l olFDical 6nift widr
17s,9q. Th. nerhyl is placed b.Neft o* inlm- aDd tqo inteFnoleulr chtorircs, 6slbM in lhe pa.kine di,gtu Fi8@ 3.tt rtblc 3.2 sho*s thlr tha hydm*a{s) on the
anilin. and 1be cycloh.xyleinc c.!e a siDild N Pd€l (ll-bord) .naDlar dj$onior incodplq c-9 (Figrrc a5) rnd bolh mot.cut.s jn cl:t (Figu,c 1,8). Borcv.r, $edtsbnjd of t.. optcing N-Pd4l dgtc ir iD lh. oppoljr. diEtions mplFn *irhcontLr c-3 b.qu& of m luiribte p.rrn.r rd lryd6!.n bondirs tr vd dd Wmlsmrcmrnons. Inlc{di lhc lolylphosphinc rcl s arts&lor td.h.* cNorin€6. Th, packing
diagnn in figuE 3.7 indicn s oEi qc ot th. tolll4 h.dryI 6tb rlE s{@ b.Mdchlo.ircs siFihr lo thc n€thyl 6 aonplex C{. Il. only nrnsbrioul s}rn ry cl.ffir(c-glid. planc) in comDld C-8 c.ups ihc Eol.cules io point ltnosl in one dnetion.
TrbL 3J: Sel6r.<l bond ldgds (4 lrd bond srl6 (&rr*t oflhc coDpkxd of*llici riDcruEs .c 0ailrbl..
Trbl.3,{: Bord o8l.r (d.sB) of lhr conpl.r.s of}hkb rtuoB,F avarrabr.
TIE t*o srb4lt iid.pd&d eo&.!l.s of th. 6tfn ri En in C-13 (1i..l3b) show simik [email protected] bodnS chmr.isi6. Th. 2{htN oitine hydosoinr€*r3 widr tlE eilie chldift . @ of d. dldi6 d dF Ftladion innn"
tuL.lLny G *Il c i|.'@kcuLdt *irh .hr.i6 of rightdins rddL. (FigN
T.l|i 3J: Bdd dirht6 to !.lLdim (A).
c{ 2.160(7) 2.25n\23) 2.3r12(22) 2.28$(22)
G9 2.160(4) 22116414) 2292t(t5' 2-2882(r5)
CnJ. 2.r55('r) 2.2J32ttt) 2J123(r2) 2.zm(t2)
c.lth 2.lltl1'l 22247(t4t 2.10r?(r3) 2.290t(t])
f2
TlE squaE pler c@diDad b.ndi of Pd 0I) show v.ry lnd. vanadd hcl*cn
ln. roleules (Tabl€ 3.6), with rhe .xc.Dtior of cl3b which dnibib i tgnili.drshoncr bond of the anilin. niEoscn 10 lh. m.l!l. Ir all doEr cls it is ob*fld lhit th.
hydrs.D bo'dins bdwccD ohlqiDes ind nitogcD (Pd-cll ) .nltBos the 6o.d di.bnc.
anin. Iisdd 6ies eFc iD@3ting surios of inh,notauLr inhciid. Lit. rl'.plFsphin.ligd4 dD asirc ligbd is |lfuS.d h. ssgad co.f@uti@ wirh BDarto th. chloD lisands (Fi8 3 r). h th. cx.nplc! or c@plac! C-9 ed Cl4, rh. hrye
crloh.xyl doieti€s on ll1. dicycloh.xyl.minc lmAe tb.m3ctv6 in r stlggcEd
conrom.l'm with Gpel to dE chloo li!.ndt ro mininin cowdins (!is. L lo). nrroaion in3lc of $€ Pd-N,H - Cl tsr. for coDplqe C,8, C-9 anq C-r4 is l, 6, ind Id.8Ec csp.cliv.ly (Trblc 3,6) whda for conpld C-13 |n. !m. losio Msl. b $l&r8. as 32 degrees du. b ine &pulsion b.w6 thc cnbro lig ds orld (U) iDd r$c
chlorc 3ubditu6t of llE siti*. If tho lggcEd otomrtion .Iow riic aniEhydbAd ro he ir pl.n. *idr lie chl@ tigrnd .s shom by ih. r6i@ ugl6, wobEfts . Edued disbne b.ero $. mift htdba.. rn<t rhc ch,oD liSr.d nor
wnhbnding a possibl. inr.dclion. Tl. hydroga .t66s on lhc anilinc aE in t3n88.rd confomtion in @npld Cn!, dd witbout llrgc noielies to [email protected] Ih. hyd.og6 rlotu e m ldg.r iD ptanc wid thc chtoo lig&& lrd th.dallJE .E longa (rrbla 3.3).
7l
ln conplexes c{, C-9 ind C-r4 rhc in-plane drgcrar ol the tsinc lieand
with thc cnloo lisard ruis.! tle p.sibility of ilta-noleub nydrqcn bmding
b"Men rh. chldinc md dE rnino trdro8d c tEviously Fcbl drdifltd chlm
lisands hrE b€en d.domhEd r"r Roon.a ct H dishrccs of 952 pn wdconsider.d shod and rhur hyrlrq.n bondin8, and inna molccular hyd68m bonding in
coppd conplcxes was Epon d iD drc nngc of 24G250 pn Lrzr. the disllne b.Nee.
rhc chldo li8'nd dd dc eiE nydrcgm is 268,25q 260 pn for cmplcxg C-3, C-9
IR rrcqu.nci€s show thc coordinlrid of phm htolin. and diil.Enl $bstitoted
phosphin6 b $c n.l.l c.nEr. 118 det il rluo orlR n.quaci.s aE irclud.d in lnc
3,4.1.2 NMR-Atrrlysis
aH, rC, rrP) NMR sp.clE show lh. coddidtim ol rfi. substirukd phoepninc!
.nd 2,9-.tiruthtl-1, lG tE nihslinc. Th. n thyl g@t next to rh. N-abd ofphcnantholirc which i cddiD.r.d to E p l.dium 6&r slrox a sigDrl d 6 = 3.21
ppD end otncr n thyl gioup! n.xt to dr fi@ N,rbn ofphcn&lhrolinc has c cnnicelshin d 6 - 3.46 ppft. &odric pFrm 6f r,!c phcmrhtolinc lirod ft i! rtE nns. ot6
= 7.71-8.83 ppm, how6, pbb,s of pnos?hirc lisauts rE iD tnc mrs. 6 = 7.21-7.60
rn @ of d. "C-NMR srera ttc 5i!n l of bcrhyl gtluFs of th? phGphitu n.r 6 = 2r.6 ppo,.nd Mo n.rhyl g6uF of ph.mtnFlim lis.nd.ft.t o -21.4 a23.4 rpn. Thc lowd ch.ni..l shin vdue ofdE ncthyl gup dr ro O. [email protected] N-.tom of pheunrhbline as conpdcd lo oth.r n.thyt goups (next 1o fi.. N-abD ofphcmn$rclin. li8!nd) clady 3ho*5 thc c@'dinrti6n of l|l. ph.turbFlim lilod b lll.prll.diun c6r?r. nc roDlic cdbon m !E ir llE 8 8. of6 = tu.7l4l.7 ppm.
Tne coodinlrion ol a phosphinc lised is indicrGd iD rh. I p-NM* spahn widl s
sigBl 6 = 26.? ppD. sinitdy, cb.ni6l lhjtu of r'! in lll mririn8 plltadiuFcoDplq6 @ld bc Erdcd. orb.. r.trrdiun [email protected] m.r.inin8 $b€tituEdphos?hincs ud 2,9 dinethyl l,l0-phd.mhblin. show . sinil& behlvid in r,\. LH rnd
3.4.t3 Silgllcryst l X-Riy Ardysitfi. crysbls of Pd i2, 9.dim€thyl-I, t0-!nd! h$li*Xtri*n-
ldylphd+hi!.)C1,, IC-221 *d. eDM hy slow diffrljon ot ed.nol inio ihc
dicnhorcthrn. elutim of ri. pil.di@ cohptd. Du* r.d crysl! *.d obt i*d.Th. ORTEP di.grlm of th. cryrut i! shoM b.tow:
n mlkx crhabic dirotu<t ,4@ pbru smFy du. io rh. b!!(t tiguds$Ltnitur.d pr'.fulhblinc od subnitu&d dftlhin s. TL bood Mgts N (tlPd-P (l)odc(2]Fkr4(l)e 172-20 (t8)&! t7.28 (8). KlfPd{(2I N(t}pd-c(D. p(ltRrc(l)!!d C(2!Fda(l) c n|mrt*.1dstft.nsL io andtlrs i.<r@Ld by
9l.42 (|6),92,76 (8),35.t|! (4) od 39.83 (r, Thc boR lostn ofpd{t(t) is lons.r rhePd-N(r) ed Pd-P(t) by 0.t74 A o.o?74 simitstr, bond tcngrh of pd-cl(2) is loglrlh4 Pd-No) , Pd-ptD by 0. | 70 A ldt 0.073 A.
T.bl. l.7r C4/tblloSnDhic ||l0 fd mDI4 Gt.
Cryc.l StsE r, spg 8roq
F, &g
RcnFdNColLcr.d/U qs
Fi'.I R iidi6 [F2o(I)]
RI
llwR2
c$HroNfPd
689-90
r30(2)
0.710?t
9.6sr0(5)
r l.05rt(or5.9855{r D
tsr.515l2)
,1.529C)
r08.@!o)
r568,6qtO
2r.461
991615621
0.0650
0.!r6!
0.1652
0ta3l
n
B.d l.ngih(A).d Bold A!sl$ O
?d0) N(r) 2140(6)
2.237(2)
2.r0(2)
Pd(r).c(2) 2.I4(2)
N(r)-Pdo)-P(l) l7].r0(r3l
N(r)?d(r)-cl(2) 91.4206)
P(rlPd(i)<(2) 92 76(8)
P(l)-Pd0)-cr(r) 8t44(l6l
N(r) Pd(r)ckr) 39.31(7)
c(rl-ld(r)<(1) r74 23(3)
T$1. 3,3: Bond lda$s lnd bond angl.s in t c.ysLl of comll.x C-22
3.5 PyrimidineBenzamideLigrnds
.rL s 9 7:r( )LN-c1 /-RtsR
R = Cl, OM., R/- Cl, Br, Mc
Flgrre 3,15: Ptdnidin -B.tuid. [L.l ro L-5]
Differcnl $6s1itutcd N-prrinidinc-bmzanid. cmpoundE weft syni\cliad wir\good yiclds of 72-34 o/0. Elcmcnlal anlltss (C, H, N) wcE dcbmined and ir was
ob*d.d $tt fon d lrd clldl.r.d klu6 .E i, cle aeE.mnl Ih? trlrir8 poirr ofill synlh.siz.d compounds !E in th. mg. ol 154-18? t.NMRAulysis
Ilc fom.rior or @npouds w.s lssed by |H-\',MR and LrC-NMR drE. H-
NMR sp.ch show rhit dE pbro of N,H Esur.s !r 6 - 8.05 ppm. nE roirticpotons of fi. b.tui<L ring @ in th€ tugc of 8.96,8.94 ppo md dr. th.r'yt n g
rcsoninccs re obswed in th. rdge of6 - ?.79-3.6t pptn Orhci conpouds foltoq iE
73
en. bd. L c6e of hdnYl subsritulod conpounds, ndlryl ptoions show al6 = 4.ll
pDb cheEicrl shii ud for n.lboxy subditukd coDpound, Fclnoxt pbhs apFat tt 6
= 1.32 ppn. rrC'NMR s?ccts! l|e Eql 0E fomlriot of t ffii& c@Doulds Th.
$.bonyl €$n.n.. was .$ign.d at 6 - I67.2 Fpn .nd the ca'lon liom of thc t€rnid.nns dircctly atllchcd lo N-H gbup was obi.fl.d d 157.? ppm. Olhcr conpolnds follow
$c se pan€n of rrc-Nli{R values. In c.* of.hlorc, brono lhd m.dvl substituGd
cornpoundE .hc elon.nes ofeftonyl gouPi rp!.!s 'r
6 = I67 20. 16?.86 dd I63 21
pps. Ito*eva, in cls of4.Nore tnd 4.d..hoxy suhsrituicd 6nP.unds lhe @rn nvl
gt@06 sho* sigels { 6 = 171.6! and 167.49 pDD. Th. cbdical 5hin5 of the minihgc.rboD atoc d. in rhc nns. of 6 = L 10.3.1 t8.8 p!n.
Palhdium (P-O) d<t base fi@ pallrdiuh (P-O) seE synth.siad accodi.s to th.
liEEtlE nclhod lrr ra ''. Firsr the lisand (ehe$oxy?hosphino) b.Mne $lronic rcid
wlr syndcaiz.n sd ch.dclerized by rl-NMR Tne 'H-NMR Esuln of litdd, !d-codpld rnd .le b& &e Pd.cmdcr s osisrai vith pEvio3ly Epon€d lulG.Pd-M€ Ep+ !!5@l. !t 6 = 021 .nd tk OM. gbup atD.r. !t 6 - 1.67 ppn. 118
rclont*e sigtul of Pd.M. in ce ol tn. b.* n* ?d{onpl.x is ii 6 - 0.4,4 ppo. ntchcmical shins of lh. m.inins DbioG a6 conplbblc to lit€mtor. vrh.s F{ rrl.
REFERENCES
l ADol.gb., A. S.i Asm, M.; zl.ng, 2.; Li, G; Sun, w' H.,,16. , CA.t. 2003,
2 Shall, B L: Brookhrt, M; Bcnnon, A. M. a. LIt Ch.n S@. 1994, 120,
4049.
L Small,B L.; Brcotirr! M. J Am.Chq.S@ 1994,120,1143.
4. B.'rovek G. t. P i Btuce, M; GihEon, V. C.; Kihbrrlsy, B. S.i Mldox, P. .t.;
Mshitui S.; McT.vish, S. J.i R..tslEw, C.; SolD, G. A.; Shmh.iB, S.;
whic. A. t. P.; willihs, D. t. L4 n. Cten. Soc. t999, | 2I , ana.
5 BliiovieL C. J PiGibso!,V CrKmb.ncy,B S.tMadox, P. J.tMcTrlish. s.
.r.r Soh'L C. A.; WuL, A. I P.; Willids, D. J. CTren Conu u. 1998, 849
6. BriroEl, G. J. P.: M!'toimi, S.; Solrn, c. A.; B.!Sn, S. P. D.; R.dshrw, C;Gibs4 V. C.; wliE, A. L P.; \viIirms, D J.i Elsogood. M R J C/rr ,!r,,000. 6,222t.
7. M!, Z. Su4 w' H.; Li, z. L ; Sh.o, C. x. I Hu, Y. L.; ri, L-H. Poltn Inr.
3 Sun,W lr; arin& S,i Zuo,w. C, k C^in.zc{d,l1,301,
9. Johi$n, L K; KilliM, C. M ; Br6tnd, M. L{r. Cl.r. 5&. 1995, I t7,64t4
10. ljinc, T. v.i !inor6, U.; bppallircn, K tKling!, Ml Ailoh, E.rtakch,M,J. Oryonoha. Ch.n. ).000,606, I l2 .nd d)ftin rfceno.s.
ll. Ji., S.; ZE& D.: an& T.: S!n, W tl.; Cba, t.: R.n, Q.; Liu, D.; Zlcng,6.jChd,w. J. A4o,on.t. Cten. 2@5, 690,1739.
12. Sun. W. H.j Th& X.; Gro, T.; Wu, Bt Zhina, W.l Ma, H. Otearcneblti5,
13. T!nl, X.; Sun, W. H.j cao, T.; Hou, J. Ch. L; Cha, W, O's@oMt. Chen.
G.@l Co tirio6: ClLlyd 5 ,6ot e$yra. pt!3s to .d; Tihc 0.5 b Tolu.m tOO
mL.'lnunit!of lO'8(ool of Cr)rh-r tD.amir.dbyCCddCC-MS. (In udtsottOJ
4.2 Oligomerizrtion of Ethyl€d€ Using Paltrdium(Il)C.talysts Containlng Mixed DoDor Ligrnds
DiftHt prlldiuD cordpl* coni.inins ob$jtur! phtunrtrolirc rdphGlhinhxazolim lisinds have b€.. r.poicd lo prcluoe edyl.n. olisond l4rl. Thc
doliil.d nebanism of cthylqe oligoicnaion by Btiodo p. .diun @nplox.scoDEiniDg 3,5'Mcr{lynalyDcEsi(plolyDt w6 iftstis{.n by Jordo,s srcuD Fl.
To thc b61of or Lwl.dg. dt is rhc tulr dm w brE usd p.lidiun cdpldevtlh nt\ed doM lig.lrL fd rn. oliS@dialin of.dlyl6..
rcc)PE
%)
5.19
2 l0 21.5
J c-4 30 0_45 063 58.1
c.l 60 IO 0. tl 39.6 015 l0.l
t c-2 l0 0.16 39.9 l0
6 c-3 l0 0.019 18.2 0.19 2t.7
0.62
8 c{ 67.8 0l? 32.1
60 0.10 78.9 2l
t0 20
II 20 2t_2
36
4.2.1 G.!.r.| Procedure for Ethyl.n. OligomenatiorA fully dricd Schlcnt luh. coilining rhc Equirod aDourl ol coblyn was
.ltcuarcd and pure.d with nitugcn dwo lincs Thcn .dryl.n. ws ch.'g.d rwioe.
FEslly dnnlled lohac was .ddcd and srircd for 5 hin, b dissotv€ the cal.tlst. A
calculated inount of ooo.blFt MAO w!! .ddd via a pr.-h.ard ftd prdried glass}'inee. lh. Mclion hixlur. wls lriRd lor 30 min und.! I rh cthyl.nc pEssre. Aiicr30 m'ruEs, rhe uction wa tcmitul.d by addine &jdificd wlrer (5% aq!ea!! HCt
solutim), IE @clion limplc vr5 an.lt&d by cC, fte yietds of otisonm w@calculalcd wirh r€ferenc. lo th. tu$ of rolv.nt prcrcqujsic $!r thc Da$ oi each
tuctio i apprcxim.t ly proponio to n! iricgnrcd ac. iD dc CC naE. rn ord.r ro
.liniBte tE chdc. of f.l* rctivir, d.Lminarioff du. b dhpotonion,lion ol $e bis-
Thc prclE n nod. of &dd ol dr. MAO coqr.lyd ii lhos in Schne 4.t.Ir. cdtalyr MAO 6Rt poduc!! an ioDic p.n vnn lh. eulyll. This i! @rsidcEd sadivc sp*i6 in lh. oliSohcriadon ofdhyl.rc.
The abMc lcriviry follow! .aording to rh. *rucruE of the ffipL*Spccficrlly tb. cmpl.x.c mry b. SrdFd ..cording b ln. smngeoeni of rh. .niftlisand. Th6 e a& abl. to sumkc lhlr th. n!tuE of dc miE liSend pkys . d€6,itiw
ole in lrow acrivc rhe 6t6ly5l colld b. bsards ol.iin oligm.ri4tion Cabllt$ c-3,
C-9, Cl1, lnd Cl,r have an aninc sisctuF wnh brg., hindenog mojcli.s that enhand
Thc citlltti. activity incr.6es i, $e cds. of chlob sulslitntd iniline irdiclting rhar !chrrsod ligdd eDvenb.nl abmd rh. n.l!l is affciits lhe &tivig of dE omplcxc6
Ih. pbduc?d olispnm @inry c@iscd of buLn.. Th. elivity of C_12' whicn
consisE of l.5dichlo'!)mline is L6 ' I or *nich i! sr!.ia $,. ib.l oI @hpllc cno
Md Cl3, {nich hld c @ $bsritutio o dE Dch ud onho posilio4 a tl.!.ibl..xDLrdon G lh{ u clccrls vil[&.viDg Gftcr of dE chloriE ndF o eiliE niSl't
cFr. .n .L.86 &6ciency on lb. bcd cd6 ehirg in ! DoE.laroptllic ndlcdtd lht mish dnftn highd slivity. Md@ftr, r cdrplq shctuE f.vs chlin
transf.s Gsulti.g in oligod.r production,
Trbl. t.tr Reicti@ prtrcL6 for oligmonznm of ethylac by Pd o.blylls.
0r^ol/Pdl500 1.00
, c-9 500 0.70
I 500 1.50
c-l I 5oo 25 t.l0c-12 500 25 1.60
c-$ J00 1.40
7 c-14 500 25 068
500 035
500 30 0sJ
l0 500
lr c,3 100 25 0.20
3(x) 25 0.25
25 0.?5
500 25 r.3
t5 500 25 052
ccid.l condnioilr 'l0' crtrol'rabn-rhir; tihc = l0 ni4pcs!rc I arni Tollde 30 hL, . - [Pd(o-iolyl),]Clr, b =
9' .l lo.tn.$yl* F.suc.
Catdysl 5 lnol Pdi Erhylcrc
frd(eiliDe)tcl2, c.8' & c"
89
Thus, w. r. rbL b pGtolic rhrtl
vinyl ir insn d into tI€ conpl.x by w.y rhar involves ihc min. lig.td.
A pEn ic.l Fi*lEr-Potu b.il..quipp.d with ! $inDs bd w.r cnns.d widr
the eralysr (20 !nol,0.012 si.nd d.i6d toludc (50 rL) in r elov. box. Th. bodle was
rsmbled dd codct d *ith oE.rhvlm lirc. Thr raction Di:tuE *B hoted at 80
"C for l5 20 min lo dissolrc the catilyd cmpl.t.ly. Thc Fi$hd-Pdd bonl. 4 .h (50
psi) was Diasuri-d wiln crhyl.n. and laror on dcnand to nainlain . pP$ur. of 4 ah(50 pi), helted ar 30oC ror 2 h ,long with oonstrnt sridina. Aner tho rcqln.d reaction
time, dE edylorc spply w6l€minrcd .rd lne boldc re lllo*cd to cel dom ro
dm lcnp@iur. Th. $lvd wa mDontcd rdd v.cuM- M.OH (20 6L) waadd.d b Pleipi!'. th. F ner. TlE pol,ffi obiincd *a *.*.n with CH:CL (20 r3nL), &.ronc (20 t 3m!) .nd M.oH (20 r rmr).
Finl of ill, conEoll€d hmopobm.liarion @clids of.rhyldc Nlg discrlc
D.\m.r ch.in. Thc$ E$lE e cmpambl. io pEviously publishcd &sulrs by our EbDprrr. Ille po\alhylcE w!5 p'ldeed in L22 g yi?ld ind nunbd lvc6sa nol4ulft s.ight(r1'./ ws €lcul.Ed &cordiry ro 's-N\rR ehich it 5.6 r rcP. Poly.dtyl4 obbincd by
br*-fie dl,lysrs hc rn ,Yn yrluc of 7.8x l0'.
4.3.2 CopolymcrtzstioD of Ethylele *itt No!-Poler Co-tnoroD€n (AtLow Ethylcb. Presure)
A plcdricd Fi6chcFtorter botrlc wa charS.d wib er.lysi5 (20 !nol; 0.012 g)
m.sndic sti ftd tolu* (50 nr) in slow box. 11 w6 Mblc4 ula our ol rhc slowbor Md cmcd ro e .thyL* $pply liR. Thc *hol. .lhyLe pply Ls *.s.scDabd r'd th.. niEoga pls Fled thbud n tbe tin6. ft. Hciio nirn@ vdh.aLd 51 30'C foi 15-20 nin ro rErc 6uE rll|r d'c @ralysr w* dislv.d cmpl.@ly
Thc co-noiotocr (15 nn.l; 1.8 g) ras.dd.d by s sliins. llon,i wirh a conlinuous
supply of .ihyld.. Lter oD rn .tlyleDe prc$ue was maiDllir.d al a aln (50 Fi) ficddioD nntur. wG hat.d.t 80oC dd8 witb .l)Mrt $irin8 tu 2 n. ARcr rhe
€qdEd titc p.rio4 n w.s .llow€n to cool dos. Thc slv6l *as *rponl.d and
MeOH (20 DL) was addcd to FEciplbr. rh. copoty6.r. nD obr.in d polynd *as
*ashed wir[ CH]ch (20r 3), i€rone (20 x 3) and M.OH (20 r 3) and dn.d undd
4.3J Copolymerizrdon of Ethyl.rc with Non-Polrr Cemoron*! (AtHlgh f,ihyle& P!.sur.)
lhmooouplo,.rd mgD.tic ly colpled sliftr and t€np€dturc atrd otltion controlled
by a P,F 4842 .orlrolla. Ar rulocLv. gh$ lind ffi chfu8.d wilh 6. c!6ly!r xrd
d.red rolu.n. (50 mL)- It wa plrccd iNi.L tb. sclo. tud va @bled TIE .urocl.Ererlor wls bDushl olt of $c slove bor.rd wls attloh€d wilh tlE controlld ind lhe
ethylcne iupply lin.. The rcnpqrtlE ws nlini.incd .! 30 oC and th. bLrion wr! 200
am. n. Eetion bnne w.s h@&d rd 15.20 mir to mat suE coDDlet. disluliotof dE c,Llt l. IlE cenonmd w.s add.d vir . !Fn'8c llon8 *idi mdtud! supply
of elhyl.o.. Tic Esotor qli pEssui-d vith cthyl.n. till rh. {icsiEd pEsor.20 !h(300 psi) wrr !cach.d. Anlr 2 h dc etbyl.n. supply was temitulcd ed de pr6sE was
was !dd.d b Feipiht @l .opolyB.r 'nE copolymer was frlatd ard wlsncd wilt
CHrCI: (20 x 3), ic€tm. 120 x , atrd McOII (20 r 3), lrd dn.d uftt r $cuub
In rh. li@toE only wo !hpl6 hrw ba fdnd, wh.E .llyl ccn@n6harc b.en u$d to pDdnce copolymcs ofrllyl llcohol and .lhyl.ndpopyt.n. by in Ilcatalysl conbinins i.denyl rnd l)rcrdyl lis.rds and i Ticvelhyl iluDiniun
s6qDichlond. olid cablyst rrrr'
H.d wc Eporl dE coFlymaianion of c6yld sd rllyl co-morm.E (illyl
elhyl clb.r, .llyl bronidc) lo produe linar oopolymers using (PO,OM'PdM(Py) as
well 6 !$. f@ calalysls (PO, OM.)PdMc. In oE crsc, w. led rlyl cGmononds
92
whm the oolar ffincriomlily is ofi CH, soup !w!v liN thc nndiotrl group r otls
b aproE i.Gdbg FoFnics ol th. dDlling copoltn6 Th' ceDo|m6 {'llvl
dtyl erhcr Ind alltl bromide) s.ft d.gas*d In $Fe cvclcs l\a!uunhrtugen) Drior b
@ RaRsnbnv. Eillrs d. lhoq in Tablc 4 5
T.bk ir,s: C@olyhdiz:tion of cthvl* with allvl brmid' 'nd 'llvl 'tnvl
ctld
G.neEl colditiont: Ctnlvsl 20 psot Tol!@
AEEI= Allyl ethyl .thd, NS _ do1 dgnii.rnl
9l
Copoltmdr.ton ot Elhylo* drb A|lJl Etlttl Eth.r
.'ff ta I
s.b.m tt2: Copolyn.rizxion of.rhylerc end allyl .thyl cdEi
Copolynsiznion of dlyl cthyt ctlEr wnh .rhyld. qd Frforn€d lnder lh. llerrion MditioB 6 us.d for rlE honoFly@rittrion of .{hyl* lo codpoE l[.
A.@din8 lo lne Butls sbown in thc tdl€ th.E w6. Eguld ie|!e in % nol
inccrponlis of @!MoB ard r d€.t.e i! Dolcul& wi8!t .rd yicld of be
F.duc wniL im@ing th. @ldi@ ot th. @mffi This tFtd 3@s @ ss@h riu to nml co@hlior of Gm6@ an r r|{) mml inc6irg ih. cd
mnoftr @@n|t!Iron, a dop in % ml ifqpodtion is obscd along wilh nolculd
rcieln $ rcl d yicu TIE high6l im'po..!d btl *bit d sa 48 96 ml ai4 tlo
mol of allyl ethyl .ther qith M, 2 9 x lo1$ calculat.n bv 'H'NMR tFcIra Aftq '10
nml of .llyl.dryl crrq. funls a.lditid d@tuero lslt d i. ! deEls€d ticld of
li*a DNE of edryleft, Enp.BsE, lnd @n6l$tion of crhyld..s '.ll.s rhc cec.ulysl modiied netn/.luninob. (MMAO). lilrd d.hibtoE ed r@riot
conditim have g@t innudc. on th. oullric lcrivity. tlis is aedding io th. mn!
objeciivc of pEenl wo*. Thc s.rcnl r..d fouowcd rg.lding this could b. dcpicied as
C-l < C-2 < c-3 < C-]|. fi.li8b.st ictility rhicv.d w..0.7 x 10" s PE Dol otcrh'ior c{ at l0 psi e rylene pressur., 1000 Al/Cr molir lio and 60'C. w. hnv. achi.led
inimsting r.sulls by fin. tunirg of !!tuctuc of crtalFl C4 oontaining 2,4,6-tin tlyl-
N-(116-{quinoxaliF3-yl)Dridin-2-y1).lhylid.nc)bondimine ti8,nd. Al 30 psi.lhylcne
prc$lE, PE 0divily ws 2 ?2 r 10" g nol ol Ci'h '. Thc lin.ar PE obtlined wd
chaaclenzd by DSC and IR. IrE DSC rBl}5b ior lE ssplcs suesested ! n€ltint
.criviry. Adiviry inces.d in rhc ordcr ot c-r4: c-9 < c-8 < c,l1 < c-13 < c-to <
cl2. Ih. high.n activity &hi.y.d wls L6 x lo's molld| Iti for Cl! (vnicn h.s
chloF subslituenls 6 6. s.b lrd prs position), Ihis night b. du. ro d .letusithdnwin3 efi@t ofchlob groDps on .nilin cEltin! D .l*ton d€fici.i n bl cdrdrc lring in t noi€ el€clrophilic DcGl end thd nishl a*ibit nbna ctivily.
lvorcover, nDE bulky substitocn6 favor chrin $nsfcr reiction! Esulriag in oligoner
producl'or. A. DcEasing prc$ur ol alhylcDo rcsults in an i.cE,$ of &rivity Thc
sla33cEd snnade or rb. dilie nrdb8.n .nd cblob subslituqrs causs an el*tloD
wilhdEwd Aon tlc fthl cdtcr ircEring th. lcrivity $ illusfated by Newn!
TIE honop.lymdtzrion of crhyld hd @polyDdaton 6f ed'yltu virh
dill*nt Fhr cmoroM Ms inv.sdgarcd uling Pd(POOM€)M{Py) dd !.* nEPd{POOM.)M. €trlys. Th. @lE oblri*d by hooopolyndiztion of .rhyld
illusrcd ln. foD.lior of til@ potycrfiyl.nc vnn bw ftdlyl bo*h.s ar 50 psi
elhylde pEsrq 80 oC, fd 2h n. potycrhylft *6 prduc.d by pd(po
OMe)Mc{Py) in 1.22 s yicld md a nunb4 rlco8c doleular weish fM, 5 6 x r Or) w6calculabd fioh |H-NMR spocrra. Howav{, r nufrbtr avhC! dotcculli wcishi ro.polyethyla€ poduo.d by ?d(?O,OMc)M. {6 ? 8 x tor undd th. !!d. ftaction
corlihoB. In o& of $. c.pobDsiador of.dyld. witn dtyl .thyl aihd, rh. hisbesr
tn.oAoblion orio for.llyl.d!yl db.r &ni.\rd wc a 8 not % with,r, = 2.9r ld !t,(0 nnol of .o-oonomr unda dE m. E.ctid andirim s ued for dc bmo-polfoerialio of .ilyld., Fu atlyl bmid. high4l incdlonrjotr drio lcni*ed wis0?3 mol % .t 15 mol of the rcsDectiv. co-homner u'dq lhc s.me rcacrim
conditioB. By utilizins r bis-ne Pdcro-oMc)M. car,lyst fd dE oopolyd.rizrio! of.lhyl* w$ borh dyl crhyl efid sd .llyl bbhidc, d iEes of i&orDodtioD nriq,t/,6 ell rs rhc yi.ld v* obeftd. ('H and rrc) NMR E3ulrs lrot.d ihe
inmrpoatior of 6-mo!@d uia ino th. h!i! brchboft of potytthyl@. In ce otallyl elhyl.tlFr, L)C-NMR Es@06 w.c funhcr rlsigned by asisnDc. ofDEpTt35as w.ll as ty HMQC I. ce oI .llyl bMid!, 1he incdpo!.tion of thc co-horcDer
wc h.!e achicvd sma tnhdng Etutll hy fin. tonins of cioDiuB dblysr. nEhiShd aoliviry w!. rchir!.n *n€n 2,4,6-Eidctiyl-N{l (6,(quinox.liD-3-yt)pFdi.e2
ylelhytidde)b€nzimino lisrnd w.s lsd lo sinlncBiz C4 c.ialyst, which is accddins to
thc mai. obj.divc oa pElenr sludy. Simihrly, in ce of pallodiun ra6lyrB, hiehei.ctivity for dn/.G oligondiario ws rchi.v.d for Cl2 colatFt vh.! md dd p@subdituled cblm milinc *c mplotrd $ lirrd. Pd(POOM.)M{Py) ablystsproducd copolyid oa.dryla. dd lyl .tnyl .dd .nd iltyl brmid..
Pd(Po-OMe)Me(Py) crldy.h an alF .oDobdcne cdryldc and allyl .lcohot. ]rEd.!il inwslisrtid of thi! sludy is in p@.$ IrE palladiuD (ll) c ilyslc cotuinins2,9ii@lhyl-1,10-phcdnth!li nd diil:E r subsrirub{t phdDhies sh@ld b.i.Bbgit.d lor.rhyl.n? ohStudiadon 6 mU s potFhzrion
LIST OF PT'BLICATIONS:
L Hu$air, R A.i Bad.hh A.; Ati.,M.,J Kor Che6 Soc.'2010,54, r'
2, A!D& M.; ad.Myi, S; Kudg, s.j B!dsh.h. A.i Sun w H.' &', ory
Ch.n.,200a,5,29G299.
3. Anotegb., S. A,; AtD4 M.; A'D& M.iLi, G i Sd, W H.',(u' J Ch.h
M,61,39..03.
4 56, W, H.; P6& H-; Li. G; Zhs& S i We& W; Yi' ,.; tuD, l/L Tt &
N., J. Oryre t- Che B,, 7l,D1, 692, 4506151 8 -
5, Ator M.; B.dsli'h, A.; ltlrdi. M.; ali, si M.lilg lvl; soh.il' M, rEA'