Methylene-Bridged Bisphosphine Monoxide Ligands for Palladium-Catalyzed Copolymerization of Ethylene and Polar Monomers

Transcription

1 Supporti Iormatio or Mthyl-Bri Bisphosphi Mooxi Lias or Pallaium-Catalyz Copolymrizatio o Ethyl a Polar Moomrs Yusuk Mitsushi, Hia Yasua, Bra P. Carrow, Shio Ito, Mioru Koayashi, Takao Tayao, Yumiko Wataa, ǁ Yoshishi Okuo, ǁ Shiya Hayashi, Juihi Kuroa, Yoshikui Okumura, a Kyoko Nozaki*, Dpartmt o Chmistry a Biotholoy, Grauat Shool o Eiri, Th Uivrsity o Tokyo, Hoo, Bukyo-ku, Tokyo , Japa Dpartmt o Chmistry, Prito Uivrsity, Prito, Nw Jrsy, Uit Stats i Japa Polyhm Corporatio, 1 Toho-ho, Yokkaihi, Mi , Japa ǁ Computatioal Si a Tholoy Iormatio Ctr, Showa Dko K.K., Ohoai, Miori-ku, Chia, Chia , Japa Istitut or Ava a Cor Tholoy, Showa Dko K.K., 2 Nakaosu, Oita, Oita , Japa 1. Exprimtal Stio 1-1 Gral S2 1-2 Prparatio o Lias a Catalysts S4 1-3 Gral Prour or Polymrizatios S16 2. NMR Sptra o Lias a Catalysts S18 3. NMR Sptra o Polymrs S30 4. X-ray Crystalloraphi Aalyss S52 S1

2 1. Exprimtal Stio 1-1 Gral Maipulatio All ratios wr arri out usi staar Shlk thiqus ur aro purii y passi throuh a hot olum pak with BASF atalyst R3-11. All opolymrizatios wr prorm i a 50-mL stailss stl autolav. Istrumtatio NMR sptra wr ror o JEOL JNM-ECS400 ( 1 H: 400 MHz, 13 C: 101 MHz, 31 P: 162 MHz, 19 F: 376 MHz) or BRUKER As500 ( 1 H: 500 MHz, 13 C: 126 MHz, 31 P: 202 MHz, 19 F: 470 MHz) NMR sptromtrs at amit tmpratur ulss othrwis ot. Chmial shit valus or protos ar rr to th rsiual proto rsoa o hloroorm- (CDCl 3, δ: 7.26) or 1,1,2,2-ttrahlorotha- 2 (C 2 D 2 Cl 4, δ: 6.00). Chmial shit valus or aros ar rr to th aro rsoas o CDCl 3 (δ: 77.2), C 2 D 2 Cl 4 (δ: 73.8), 1,1,2,2-ttrahlorotha (δ: 74.2) or 1,2,4-trihloroz (δ: 127.9). Chmial shit valus or phosphoruss ar rr to th phosphorus rsoa o 85% H 3 PO 4 as a xtral staar. Chmial shit valus or luoris ar rr to th luori rsoa o CF 3 C 6 H 5 (δ: 62.8 i CDCl 3 ) [i] as a xtral staar. Quatitativ 13 C NMR aalyss o polymrs wr prorm o a. 15 wiht% solutios o th polymrs a a M Cr(aa) 3 as a rlaxatio at i 1,1,2,2-ttrahlorotha or C 2 D 2 Cl 4 ulok at 120 C usi a 30 puls o 16.8 µs, a sptral with o 30 khz, a rlaxatio tim o 2 s, a aquisitio tim = 1.1 s, a ivrs-at oupli (BRUKER As500).[ii,iii] Siz xlusio hromatoraphy (SEC) aalyss wr arri out with a Tosoh istrumt (HLC-8121GPC/HT) quipp with two SEC olums (Tosoh TSKl GMHHR-H(S)HT) a a rrativ ix (RI) ttor y luti th olums with 1,2-ihloroz at 1.0 ml/mi at 145 C. Molular wihts wr trmi usi arrow polystyr staars a wr orrt or polythyl y uivrsal aliratio usi th Mark Houwik paramtrs o Rui: K = m 3 / a α = 0.67 or polystyr a K = m 3 / a α = 0.69 or LLDPE.[iv] X-ray rystalloraphi aalysis was prorm o a Riaku Varimax with Satur iratomtr. Elmtal aalysis was prorm y th Miroaalytial Laoratory, Dpartmt o Chmistry, Grauat Shool o Si, Th Uivrsity o Tokyo, or y O-stop Shari Faility Ctr or Futur Dru Disovris, Grauat Shool o Pharmautial Sis, Th Uivrsity o Tokyo. Hih rsolutio mass sptra wr ror o JEOL JMS-T100LP AuTOF LC-plus. [i] So, S.; Taylor, J. B.; Gray, M. F. Chm. Commu. 2013, 49, [ii] (a) Gua, Z.; Cotts, P. M.; MCor, E. F.; MLai, S. J. Si, 1999, 283, () Cotts, P. M.; Gua, Z.; MCor, E. F.; MLai, S. J. Maromoluls, 2000, 33, [iii] Raall, J. C.; Ru, C. J.; Klhtrmas, M.; Grory, B. H. Maromoluls, 1992, 25, [iv] Grishpu, V.; Rui, A. Makrom. Chm., Rapi Commu., 1985, 6, S2

3 Matrials Ahyrous ihloromtha, ithyl thr, hxa, ttrahyroura (THF), a tolu wr purhas rom Kato Chmial Co. I. (Kato) a purii y th mtho o Paor t al.[v] Ethyl (>99.9%) was purhas rom Takahiho Chmial Iustrial Co., Lt., ri, a oxyat y passi throuh olums. Th ollowi rats wr purhas rom Tokyo Chmial Iustry, Co., Lt. (TCI) a purii y istillatio ovr CaH 2 : allyl atat, viyl atat, utyl viyl thr, aryloitril, mthyl arylat, a mthyl mtharylat. Th ollowi rats wr purhas a us as riv: utyllithium (BuLi) i hxa (Kato), s-utyllithium (s-buli) i ylohxa (Kato), trt-utyllithium (t-buli) i pta (Kato), trimthylphosphi oxi (Wako), hloroiisopropylphosphi (Alrih), i-trt-utylhlorophosphi (Wako), soium ttrakis[3,5-is(triluoromthyl)phyl]orat (NaBAr F 4, Matrix Sitii), 2,6-lutii (TCI), hlorois(2-mthoxyphyl)phosphi (Alrih). Th ollowi ompous wr prpar aori to th prours i litratur: hlorio(yloota-1,5-i)(mthyl)pallaium (PMCl(o)),[ vi ], hlorois(2-triluoromthylphyl)phosphi,[ vii ] is(i-trt-utylphosphayl)mtha,[vii] i-trt-utyl(mthyl)phosphi oxi[viii]. [v] Paor, A. B.; Giarllo, M. A.; Grus, R. H.; Ros, R. K.; Timmrs, F. J. Oraomtallis, 1996, 15, [vi] Rülk, R. E.; Ersti, J. M.; Spk, A. L.; Elsvir, C. J.; va Luw, P. W. N. M.; Vriz, K. Ior. Chm., 1993, 32, [vii] Eisträr, F.; Göthlih, A.; Grur, I.; Hiss, H.; Kir, C. A.; Krür, C.; Nothis, J. U.; Romir, F.; Shrha, G.; Shultz, M.; Strau, B. F.; Volla, M. A. O.; Homa, P. Nw. J. Chm. 2003, 27, [viii] Li, C.; Ch, T.; Li, B.; Xiao, G.; Ta, W. Aw. Chm. It. E. 2015, 54, S3

4 1-2. Prparatio o Lias a Catalysts (SP-4-2)-(i-trt-utyl{[is(2-mthoxyphyl)phosphio-κP]mthyl}phosphi oxi-κo)(hlorio)(mthyl)pallaium (2a): To a solutio o i-trt-utyl(mthyl)phosphi oxi (76 m, 0.43 mmol, 1.0 quiv) i THF (1.6 ml) was a BuLi (1.63 M solutio i hxa, 0.29 ml, 0.47 mmol, 1.1 quiv) at 78 C a th ratio mixtur was stirr or 70 miuts at 78 C. Th rsulti solutio was trasrr to a Shlk tu otaii hlorois(2-mthoxyphyl)phosphi (120 m, 0.43 mmol, 1.0 quiv) a th ratio mixtur was stirr or 15 miuts at 78 C. Th th ry i ath was rmov a th ratio mixtur was stirr at amit tmpratur or 14 hours. Th ratio mixtur was warm to 60 C a stirr or 4.5 hours at 60 C. Th ratio was quh with watr (10 µl) a solvt was rmov i vauo to aor th ru mixtur o {[(2-OMC 6 H 4 ) 2 P]CH 2 }P(O)tBu 2 (a. 40% purity as o 31 P{ 1 H} NMR, a mmol o th titl prout). 31 P{ 1 H} NMR (THF, 162 MHz) δ: 57.0 (, J = 26 Hz), 32.9 (, J = 26 Hz). Nxt, to th mixtur o ru {[(2-OMC 6 H 4 ) 2 P]CH 2 }P(O)tBu 2 (a mmol o th titl prout) a PMCl(o) (50 m, 0.19 mmol, 1.1 quiv) was a ihloromtha (1.5 ml) at amit tmpratur a th ratio mixtur was stirr or 7 hours at amit tmpratur. Th, th suspsio was iltr throuh a pa o Clit to rmov th orm lithium salt a vaporat to rmov th volatil mattrs. Th rsulti ummy soli was wash with hxa a th rmaii soli was issolv ito ihloromtha aai. Th suspsio was iltr throuh a syri iltr a th rrystallizatio rom ihloromtha/ithyl thr aor th titl prout i 33% yil (82 m, 0.14 mmol) ovr two stps. Althouh th prout otai a small amout o impuritis, w us it or th sythsis o 3a without urthr puriiatio. 1 H NMR (CDCl 3, 500 MHz) δ: 7.76 (r, 2H), 7.51 (, J = 7.8 Hz, 7.8 Hz, 2H), (m, 4H), 3.90 (s, 6H), 3.38 (, J = 13.3, 6.0 Hz, 2H), 1.21 (, J = 14.3 Hz, 18H), 0.39 (, J = 3.4 Hz, 3H); 13 C{ 1 H} NMR (CDCl 3, 126 MHz) δ: (s, 2C), (r, 2C), (s, 2C), (s, 1C), (s, 1C), (, J = 3 Hz, 1C), (, J = 3 Hz, 1C), (s, 1C), (s, 1C), 56.1 (s, 2C), 36.3 (, J = 59 Hz, 2C), 26.8 (s, 6C), 21.4 (, J = 49, 18 Hz, 1C), 4.7 (, J = 2 Hz, 1C); 31 P{ 1 H} NMR (CDCl 3, 202 MHz) δ: 83.0 (, J = 10 Hz), 31.3 (, J = 10 Hz); HRMS (ESI-TOF) m/z al or C 24 H 37 O 3 P 2 P [M Cl] ; ou S4

5 (SP-4-2)-(i-trt-utyl{[is(2-triluoromthylphyl)phosphio-κP]mthyl}phosphi oxi-κo)(hlorio)(mthyl)pallaium (2): To a solutio o i-trt-utyl(mthyl)phosphi oxi (0.40, 2.3 mmol, 1.0 quiv) i THF (10 ml) was a BuLi (2.5 M i hxa, 0.90 ml, 2.3 mmol, 1.0 quiv) at 78 C a th mixtur was stirr or 1 hour at 78 C. Th a solutio o hlorois(2-triluoromthylphyl)phosphi (0.89, 2.5 mmol, 1.1 quiv) i THF (5 ml) was slowly a to th ratio mixtur. Th ratio mixtur was allow to warm to 20 C a stirr or 12 hours at 20 C, a th th ratio was quh with watr (15 ml). Th orai layr was sparat a th aquous layr was xtrat with thyl atat (15 ml 3). Th omi orai phas was wash with ri (45 ml), ri ovr ahyrous Na 2 SO 4, a otrat i vauo. Th rsiu was purii y silia l olum hromatoraphy (ihloromtha/mthaol = 20:1) twi to aor {[(2-CF 3 C 6 H 4 ) 2 P]CH 2 }P(O)tBu 2 (190 m, 0.38 mmol) i 17% yil as a olorlss soli. 31 P{ 1 H} NMR (CDCl 3, 162 MHz) δ: 60.0 (s), 23.9 (sp, J = 48 Hz). Th sam prour was rpat o a 500 m sal to otai 175 m o {[(2-CF 3 C 6 H 4 ) 2 P]CH 2 }P(O)tBu 2 (Six aths, avra yil). Nxt, to a solutio o omi {[(2-CF 3 C 6 H 4 ) 2 P]CH 2 }P(O)tBu 2 (470 m, 0.95 mmol) i ihloromtha (6.3 ml) was a a solutio o PMCl(o) (250 m, 0.95 mmol, 1.0 quiv) i ihloromtha (6.3 ml) at amit tmpratur, a th ratio mixtur was stirr or 5 miuts at amit tmpratur. Th rsulti solutio was otrat to hal volum i vauo a wash with hxa (3.8 ml 3) to otai th titl prout (639 m). Si it was iiult to ompltly rmov rsiual ihloromtha rom th rsulti soli, w us it or th xt stp without urthr puriiatio. 1 H NMR (CDCl 3, 500 MHz, 60 C) δ: 9.32 (s, 1H), (m, 7H), 3.61 (r, 1H), 3.13 (r, 1H), 1.35 (r, 9H), 1.09 (r, 9H), 0.56 (, J = 4.0 Hz, 3H); 13 C{ 1 H} NMR (CDCl 3, 126 MHz, 60 C) δ: 141.2, 137.8, 132.5, 131.5, 131.2, 129.7, 128.2, 125.6, 125.1, 123.3, 122.9, 121.2, 120.8, 37.3 (, J = 96, 66 Hz, 1C), 27.0 (s, 6C), 25.8 (, J = 45, 10 Hz, 2C), 0.1 (s); (Not: Th sials at aromati rio oul ot ully assi u to omplx J-oupli); 19 F NMR (CDCl 3, 470 MHz, 60 C) δ: 55.0 (s), 55.6 (s); 31 P{ 1 H} NMR (CDCl 3, 202 MHz, 60 C) δ: 83.1 (, J = 15 Hz), 48.2 (s); HRMS (ESI-TOF) m/z al or C 24 H 31 F 6 OP 2 P [M Cl] ; ou S5

6 (SP-4-2)-{i-trt-utyl[(iisopropylphosphio-κP)mthyl]phosphi oxi-κo}(hlorio)(mthyl)pallaium (2): To a solutio o i-trt-utyl(mthyl)phosphi oxi (177 m, 1.0 mmol, 1.0 quiv) i THF (3.3 ml) was a t-buli (1.60 M solutio i hxa, 0.67 ml, 1.1 mmol, 1.1 quiv) at 78 C a th ratio mixtur was stirr or 2 hours at 78 C. Th rsulti solutio was trasrr to a Shlk tu otaii hloroiisopropylphosphi (0.32 ml, 2.0 mmol, 2.0 quiv) a th ratio mixtur was stirr or 2 hours at 78 C. Th th ry i ath was rmov a th ratio mixtur was stirr or 2.5 hours at amit tmpratur. Th solvt was rmov i vauo a th rsulti ummy soli was ri at 70 C i vauo to otai th ru mixtur o [(ipr 2 P)CH 2 ]P(O)tBu 2 (a. 50% purity as o 31 P{ 1 H} NMR, a mmol o th titl prout). 31 P{ 1 H} NMR (THF, 162 MHz) δ: 57.0 (, J = 13 Hz), 3.8 (, J = 17 Hz). Nxt, to th mixtur o ru [(ipr 2 P)CH 2 ]P(O)tBu 2 (a mmol o th titl prout) a ihloromtha (3.5 ml) was a PMCl(o) (150 m, 0.55 mmol, 1.1 quiv) at amit tmpratur a th ratio mixtur was stirr or 21 hours at amit tmpratur. Th, th suspsio was iltr throuh a pa o Clit to rmov th orm lithium salt a vaporat to rmov th volatil mattrs. Th ru prout was issolv ito ihloromtha aai a th rrystallizatio rom ihloromtha/ithyl thr aor th titl prout i 45% yil (200 m, 0.45 mmol) ovr two stps. Sil rystals suital or X-ray iratio aalysis wr row rom vapor iusio o pta ito th solutio o 2 i 1,1,2,2-ttrahlorotha. 1 H NMR (CDCl 3, 500 MHz) δ: 2.28 (, J = 7.0 Hz, 2H), 2.19 (, J = 9.5, 7.6 Hz, 2H), 1.41 (, J = 14.3 Hz, 18H, ovrlapp with th sial at δ = 1.39), 1.39 (, J = 7.0 Hz, 3H, ovrlapp with th sial at δ = 1.41), 1.36 (, J = 7.0 Hz, 3H), 1.32 (, J = 7.0 Hz, 3H), 1.29 (, J = 7.3 Hz, 3H), 0.76 (, J = 1.8 Hz, 3H); 13 C{ 1 H} NMR (CDCl 3, 126 MHz) δ: 36.9 (, J = 58 Hz, 2C), 27.6 (s, 6C), 26.2 (, J = 23, 2 Hz, 2C), 19.6 (s, 2C), 19.2 (s, 2C), 15.8 (, J = 50, 8 Hz, 1C), 10.8 (, J = 4 Hz, 1C); 31 P{ 1 H} NMR (CDCl 3, 202 MHz) δ: 82.0 (, J = 7 Hz), 52.3 (, J = 7 Hz); Aal. Cal or C 16 H 37 ClOP 2 P, C, 42.77; H, 8.30; ou: C, 42.48; H, S6

7 (SP-4-2)-{i-trt-utyl[(i-trt-utylphosphio-κP)mthyl]phosphi oxi-κo}(hlorio)(mthyl)pallaium (2): To a solutio o is(i-trt-utylphosphiyl)mtha (2.50, 8.2 mmol, 1.0 quiv) i Et 2 O (30 ml) was a aquous HCl (12 M, 1.4 ml, 16.4 mmol, 2.0 quiv) at 0 C. A whit pripitat was orm a th rsulti suspsio was stirr at 0 C or 1 hour. Th solvt was rmov i vauo a th watr (15 ml) was a to th rsulti soli to iv a olorlss solutio. Th, th mixtur o aquous H 2 O 2 (8.8 M, 0.89 ml, 7.8 mmol, 1.0 quiv) a NaOH (1.78, 44.5 mmol, 5.4 quiv) i watr (3 ml) was quikly a to th solutio. Th rsulti mixtur was stirr or 1 hour at 15 C. Th orm pripitats wr ollt y iltratio a ri i vauo to otai a yllow soli. Th yllow soli was rrystalliz rom ithyl thr to otai [(tbu 2 P)CH 2 ]P(O)tBu 2 ( mmol) i 46% yil. 31 P{ 1 H} NMR (CDCl 3, 162 MHz) δ: 58.6 (, J = 21 Hz), 20.1 (, J = 21 Hz). Nxt, to th mixtur o [(tbu 2 P)CH 2 ]P(O)tBu 2 (160 m, 0.50 mmol, 1.0 quiv) a PMCl(o) (150 m, 0.55 mmol, 1.1 quiv) was a ihloromtha (3.5 ml) at amit tmpratur a th ratio mixtur was stirr or 5 hours at amit tmpratur. Atr th ihloromtha was rmov i vauo, th rrystallizatio rom ihloromtha/hxa aor th titl prout i 94% yil (220 m, 0.47 mmol). Althouh th prout otai a small amout o impuritis, w us it or th sythsis o 3 without urthr puriiatio. 1 H NMR (CDCl 3, 500 MHz) δ: 2.32 (, J = 8.5, 8.5 Hz), 1.49 (, J = 6.4 Hz), 1.46 (, J = 6.4 Hz), 1.00 (, J = 1.5 Hz); 13 C{ 1 H} NMR (CDCl 3, 202 MHz) δ: 37.8 (, J = 14, 3 Hz, 2C), 37.6 (, J = 57 Hz, 2C), 30.8 (, J = 5 Hz, 6C), 28.6 (s, 6C), 17.2 (, J = 50, 3 Hz, 1C), 12.1 (, J = 4 Hz, 1C); 31 P{ 1 H} NMR (CDCl 3, 202 MHz) δ: 81.4 (, J = 7 Hz), 63.9 (, J = 7 Hz); Aal. Cal or C 18 H 41 ClOP 2 P, C, 45.29; H, ou: C, 44.93; H, S7

8 (SP-4-2)-{[(i-trt-utylphosphio-κP)mthyl]imthylphosphi oxi-κo}(hlorio)(mthyl)pallaium (2): To a solutio o trimthylphosphi oxi (3.0, 32.6 mmol) i THF (180 ml) was a t-buli (1.6 M, 20.4 ml, 32.6 mmol, 1.0 quiv) at 78 C. Th mixtur was stirr at 78 C or 1 hour. Th, i-trt-utyl(hloro)phosphi (5.89, 32.6 mmol, 1.0 quiv) was a to th mixtur. Th, th ry i ath was rmov a th ratio mixtur was stirr at amit tmpratur or 16 hours to aor a olorlss solutio. Th solvt was rmov i vauo a th rsulti rsiu was xtrat with ihloromtha (50 ml 2). Th omi ihloromtha solutio was wash with watr (20 ml 2), ri ovr ahyrous Na 2 SO 4, iltr, a otrat i vauo. Th otai soli was urthr wash with ithyl thr (5.0 ml). Whit pripitats wr th ollt y iltratio a ri i vauo to otai [(tbu 2 P)CH 2 ]P(O)M 2 (2.70, 11.4 mmol) i 35% yil. 31 P{ 1 H} NMR (CDCl 3, 162 MHz) δ: 66.4 (s), 43.7 (sp, J = 10 Hz). Nxt, to th mixtur o [(tbu 2 P)CH 2 ]P(O)M 2 (71 m, 0.30 mmol, 1.0 quiv) a PMCl(o) (88 m, 0.33 mmol, 1.1 quiv) was a ihloromtha (2.0 ml) at amit tmpratur a th ratio mixtur was stirr or 21 hours at amit tmpratur. Atr th volatil mattrs wr rmov i vauo, th rsulti soli was purii y rrystallizatio rom ihloromtha/ithyl thr. Th otai soli was urthr rrystalliz rom atoitril/ithyl thr to otai th titl prout i 75% yil (89 m, 0.23 mmol). Althouh th prout otai a small amout o impuritis, w us it or th sythsis o 3 without urthr puriiatio. 1 H NMR (CDCl 3, 500 MHz) δ: 2.24 (, J = 9.5, 9.5 Hz, 2H), 1.77 (, J = 12.8 Hz, 6H), 1.41 (, J = 14.3 Hz, 18H), 1.02 (, J = 1.5 Hz, 3H); 13 C{ 1 H} NMR (CDCl 3, 126 MHz) δ: 36.2 (, J = 15, 3 Hz, 2C), 29.6 (, J = 5 Hz, 6C), 26.0 (, J = 67, 7 Hz, 1C), 18.4 (, J = 71 Hz, 2C), 10.6 (, J = 4 Hz, 1C); 31 P{ 1 H} NMR (CDCl 3, 202 MHz) δ: 59.6 (, J = 15 Hz), 59.0 (, J = 15 Hz); HRMS (ESI-TOF) m/z al or C 24 H 37 O 3 P 2 P [M Cl] ; ou S8

9 (SP-4-2)-(hlorio)(mthyl)[imthyl({is[(1R,2S,5R)-5-mthyl-2-(propa-2-yl)ylohxyl]pho sphio-κp}mthyl)phosphi oxi-κo]pallaium (2): To th mixtur o trimthylphosphi oxi (92 m, 1.0 mmol, 1.0 quiv) a THF (3.2 ml) was a s-buli (1.05 M i a mixtur o ylohxa a hxa) ropwis at 78 C. Th rsulti whit suspsio was trasrr via aula to th mixtur o hloroi[(1r,2s,5r)-2-isopropyl- 5-mthylylohxa-1-yl]phosphi (380 m, 1.1 mmol, 1.1 quiv) i THF (3.2 ml) at 78 C. Th ry i ath was rmov atr 10 mi a th ratio mixtur was stirr or 2 hours at amit tmpratur. Th, th ratio mixtur was warm to 60 C a stirr or 3 hours. Th ratio mixtur was urthr warm to 70 C a stirr or 20 hours. Th ratio mixtur was quh with ass watr (20 µl) a th solvt was rmov i vauo. Dihloromtha (10 ml) was a to th rsulti soli a th whit suspsio was wash with ass watr (10 ml 3). Th omi aquous phas was xtrat with ihloromtha (10 ml) a th omi orai phas was iltr throuh a pa o Clit/Na 2 SO 4 /MSO 4. Th solvt was rmov i vauo to otai th ru [(M) 2 P]CH 2 }P(O)M 2 (349.8 m, purity a. 83%, a mmol). 31 P{ 1 H} NMR (ihloromtha) δ: 40.6 (, J = 65 Hz), 35.4 (, J = 61 Hz) Nxt, to a mixtur o [(M) 2 P]CH 2 }P(O)M 2 (349.8 m) a ihloromtha (6.0 ml) was a PMCl(o) (230 m, 0.87 mmol) a th rsulti yllow solutio was stirr at amit tmpratur or 1 hour. Th, th ratio mixtur was iltr throuh a syri iltr a th rrystallizatio rom ihloromtha/ithyl thr aor th titl ompou i 24% yil (130 m, 0.24 mmol) ovr two stps as a olorlss soli. 1 H NMR (CDCl 3, 500 MHz) δ: 4.10 (r, 1H), (m, 3H), 2.22 (, J = 9.8, 9.8 Hz, 1H), 2.15 (, J = 18.5, 10.5 Hz, 1H), 2.01 (, J = 11.0, 11.0, 11.0 Hz, 1H), (m, 3H), 1.75 (r, 2H), 1.67 (, J = 12.8 Hz, 6H), 1.57 (r, 1H, ovrlapp with a proto sial o rsiual watr), 1.45 (r, 1H), (m, 30H); 13 C{ 1 H} NMR (CDCl 3, 126 MHz) δ: 48.0 (, J = 5 Hz, 1C), 44.4 (s, 1C), 40.8 (, J = 21, 4 Hz, 1C), 36.5 (, J = 7 Hz, 1C), 36.2 (s, 1C), 34.8 (s, 1C), 34.5 (s, 1C), 34.5 (, J = 21, 3 Hz, 1C), 34.0 (, J = 10 Hz, 1C), 33.2 (, J = 7 Hz, 1C), 28.2 (, J = 5 Hz, 1C), 27.5 (, J = 10 Hz, 1C), 27.2 (, J = 67, 8 Hz, 1C), 25.3 (, J = 23 Hz, 1C), 25.3 (s, 1C), 23.0 (s, 1C), 22.9 (s, 1C), 22.3 (s, 1C), 22.1 (s, 1C), 18.7 (, J = 70 Hz, 1C), 18.2 (, J = 70, 3 Hz, 1C), 16.8 (s, 1C), 16.5 (s, 1C), 9.7 (, J = 4 Hz, 1C); 31 P{ 1 H} NMR (CDCl 3, 202 MHz) δ: 61.9 (, J = 17 Hz), 28.7 (, J = 17 Hz); Aal. Cal or C 24 H 49 ClOP 2 P, C, 51.71; H, ou: C, 51.47; H, 8.66; HRMS (ESI-TOF) m/z al or C 24 H 49 OP 2 P [M Cl] ; ou Sil rystals suital or X-ray aalysis was row rom vapor iusio o pta ito a solutio o 2 i 1,1,2,2-ttrahlorotha. S9

10 (SP-4-4)-[(i-trt-utyl{[is(2-mthoxyphyl)phosphio-κP]mthyl}phosphi oxi-κo)(mthyl)(2,6-imthylpyrii)pallaium]{ttrakis[3,5-is(triluoromthyl)phyl] orat} (3a): To a solutio o 2a (57 m, 0.1 mmol, 1.0 quiv) a 2,6-lutii (17.5 µl, 0.15 mmol, 1.5 quiv) i ihloromtha (3.0 ml) was a NaBAr F 4 (89 m, 0.1 mmol, 1.0 quiv) at amit tmpratur a th ratio mixtur was stirr or 14 hours at amit tmpratur. Th th ratio mixtur was iltrat throuh a syri iltr to rmov th orm soium salt a vaporat to rmov th volatil mattrs. Th ru matrial was issolv ito ihloromtha (a. 3.0 ml) aai a rrystalliz rom ihloromtha/hxa to otai th titl prout i 79% (120 m, mmol) yil. 1 H NMR (CDCl 3, 500 MHz) δ: (m, 17H), 7.18 (, J = 7.6 Hz, 2H), (m, 4H), 3.90 (s, 6H), 3.39 (, J = 13.7, 5.8 Hz, 2H), 3.05 (s, 6H), 1.11 (, J = 14.6 Hz, 18H), 0.04 (, J = 3.4 Hz, 3H); 13 C{ 1 H} NMR (CDCl 3, 126 MHz) δ: (m, 4C), (s, 2C), (s, 2C), (s, 1C), (r, 2C), (s, 2C), (s, 8C), (qq, J = 31 Hz, 3 Hz, 8C), (q, J = 272 Hz, 8C), (s, 1C), (s, 1C), (s, 1C), (s, 1C), (sptt, J = 4 Hz, 4C), (, J = 3 Hz, 1C), (, J = 3 Hz, 1C), (s, 1C), (s, 1C), 55.9 (s, 2C), 36.3 (, J = 57 Hz, 2C), 26.6 (s, 6C), 26.4 (s, 2C), 22.5 (, J = 49, 18 Hz, 1C), 5.6 (, J = 5 Hz, 1C); 31 P{ 1 H} NMR (CDCl 3, 202 MHz) δ: 91.3 (, J = 10 Hz), 31.2 (, J = 12 Hz); 19 F NMR (CDCl 3, 470 MHz) δ: 62.5 (s); Aal. Cal or C 63 H 58 BF 24 NO 3 P 2 P, C, 50.04; H, 3.87; N, ou: C, 49.73; H, 4.00; N, S10

11 (SP-4-4)-[(i-trt-utyl{[is(2-triluoromthylphyl)phosphio-κP]mthyl}phosphi oxi-κo)(mthyl)(2,6-imthylpyrii)pallaium]{ttrakis[3,5-is(triluoromthyl)phyl] orat} (3): To a solutio o 2 (639 m, 0.98 mmol, 1.0 quiv) a 2,6-lutii (110 µl, 0.95 mmol, 0.97 quiv) i ihloromtha (10 ml) was a a suspsio o NaBAr F 4 (837 m, 0.95 mmol, 0.97 quiv) a Na 2 SO 4 (1.0 ) i ihloromtha (5 ml) at amit tmpratur. Th ratio mixtur was stirr or 10 miuts at amit tmpratur. Th ratio mixtur was iltr throuh a pa o Clit to rmov th orm soium salt a vaporat to rmov th volatil mattrs. Th ru matrial was issolv ito ihloromtha aai a rrystalliz rom ihloromtha/ithyl thr to otai th titl prout i 55% yil (852 m, 0.54 mmol). 1 H NMR (CDCl 3, 500 MHz) δ: 8.98 (, J = 12.8 Hz, 1H), (r, 2H), 7.79 (r, 2H), 7.72 (s, 8H), (m, 2H), 7.51 (s, 4H), 7.44 (, J = 7.2, 7.2 Hz, 1H), 7.17 (r, 2H), 6.89 (r, 1H), 3.76 (, J = 26.1, 12.1 Hz, 1H), (m, 4H), 2.89 (s, 3H), 1.31 (, J = 15.0 Hz, 9H), 0.91 (, J = 14.6 Hz, 9H), 0.17 (, J = 3.1 Hz, 3H); 13 C{ 1 H} NMR (CDCl 3, 126 MHz) δ: (m, 4C), (s, 1C), (s, 1C), (r), (s, 1C), (s, 8C a othr sials), 134.2, 132.9, 132.8, 132.1, 132.0, 131.9, 131.9, 131.7, 131.4, 131.1, 129.8, (qq, J = 31, 3 Hz, 8C a othr sials), 128.5, (q, J = 273 Hz, 8C), (q, J = 275 Hz, 1C), (q, J = 275 Hz, 1C), 123.5, , 123.3, (sptt, J = 4 Hz, 4C) (Not: Th sials at aromati rio oul ot ully assi u to omplx J-oupli), 37.8 (, J = 57 Hz, 1C), 36.6 (, J = 57 Hz, 1C), 26.9 (s, 3C), 26.6 (s, 5C), 26.3 (s, 1C), 1.9 (, J = 2 Hz, 1C); 31 P{ 1 H} NMR (CDCl 3, 202 MHz) δ: 93.1 (, J = 12 Hz), 52.2 (s); 19 F NMR (CDCl 3, 470 MHz) δ: 54.6 (s), 54.6 (r s), 62.5 (s); Aal. Cal or C 63 H 52 BF 30 NOP 2 P, C, 47.64; H, 3.30; N, ou: C, 47.49; H, 3.52; N, S11

12 (SP-4-4)-({i-trt-utyl[(iisopropylphosphio-κP)mthyl]phosphi oxi-κo}(mthyl)(2,6-imthylpyrii)pallaium){ttrakis[3,5-is(triluoromthyl)phyl] orat} (3): To a solutio o 2 (90 m, 0.2 mmol, 1.0 quiv) a 2,6-lutii (35 µl, 0.3 mmol, 1.5 quiv) i ihloromtha (5.0 ml) was a NaBAr F 4 (180 m, 0.2 mmol, 1.0 quiv) at amit tmpratur a th ratio mixtur was stirr or 12 hours at amit tmpratur. Th th ratio mixtur was iltrat throuh a syri iltr to rmov th orm soium salt a vaporat to rmov th volatil mattrs. Th ru matrial was issolv ito ihloromtha (a. 4.0 ml) aai a rrystalliz rom ihloromtha/hxa to otai th titl prout i 81% (220 m, 0.16 mmol) yil. 1 H NMR (CDCl 3, 500 MHz) δ: 7.71 (r, 8H), 7.62 (t, J = 7.6 Hz, 1H), 7.52 (s, 4H), 7.15 (, J = 7.6 Hz, 2H), 2.94 (s, 6H), 2.36 (sptt o oult, J = 7.0, 7.0 Hz, 2H), 2.25 (, J = 10.7, 7.0 Hz, 2H), 1.39 (, J = 7.3 Hz, 3H), 1.36 (, J = 7.0 Hz, 3H), 1.36 (, J = 7.3 Hz, 3H), 1.33 (, J = 7.0 Hz, 3H), 1.25 (, J = 14.6 Hz, 18H), 0.35 (, J = 2.7 Hz, 3H); 13 C{ 1 H} NMR (CDCl 3, 126 MHz) δ: (m, 4C), (s, 2C), (s, 1C), (s, 8C), (qq, J = 31 Hz, 3 Hz, 8C), (q, J = 272 Hz, 8C), (s, 1C), (s, 1C), (sptt, J = 4 Hz, 4C), 36.9 (, J = 58 Hz, 2C), 27.1 (, J = 3 Hz, 1C), 26.9 (, J = 4 Hz, 1C), 26.9 (s, 6C), 26.4 (s, 2C), 20.3 (s, 2C), 18,8 (s, 2C), 15.5 (, J = 50, 8 Hz, 1C), 10.9 (, J = 5 Hz, 1C); 31 P{ 1 H} NMR (CDCl 3, 202 MHz) δ: 91.8 (, J = 7 Hz), 55.3 (, J = 7 Hz); 19 F NMR (CDCl 3, 470 MHz) δ: 62.4 (s); Aal. Cal or C 55 H 58 BF 24 NOP 2 P, C, 47.72; H, 4.22; N, ou: C, 47.80; H, 4.27; N, S12

13 (SP-4-4)-({i-trt-utyl[(i-trt-utylphosphio-κP)mthyl]phosphi oxi-κo}(mthyl)(2,6-imthylpyrii)pallaium){ttrakis[3,5-is(triluoromthyl)phyl] orat} (3): To a solutio o 2 (150 m, 0.31 mmol, 1.0 quiv) a 2,6-lutii (55 µl, 0.47 mmol, 1.5 quiv) i ihloromtha (7.0 ml) was a NaBAr F 4 (280 m, 0.31 mmol, 1.0 quiv) at amit tmpratur a th ratio mixtur was stirr or 13 hours at amit tmpratur. Th th ratio mixtur was iltrat throuh a syri iltr to rmov th orm soium salt a vaporat to rmov th volatil mattrs. Th ru matrial was issolv ito ihloromtha (a. 5.0 ml) aai a rrystalliz rom ihloromtha/hxa to otai th titl prout i 94% (220 m, 0.16 mmol) yil. 1 H NMR (CDCl 3, 500 MHz) δ: 7.71 (sptt, J = 2.3 Hz, 8H), 7.61 (t, J = 7.8 Hz, 1H), 7.52 (r s, 4H), 7.15 (, J = 7.6 Hz, 2H), 2.97 (s, 6H), 2.42 (, J = 9.6, 7.8 Hz, 2H), 1.48 (, J = 14.3 Hz, 18H), 1.29 (, J = 14.3 Hz, 18H), 0.56 (, J = 2.1 Hz, 3H); 13 C{ 1 H} NMR (CDCl 3, 126 MHz) δ: (m, 4C), (s, 2C), (s, 1C), (s, 8C), (qq, J = 31 Hz, 3 Hz, 8C), (q, J = 272 Hz, 8C), (s, 1C), (s, 1C), (sptt, J = 4 Hz, 4C), 38.2 (, J = 15, 2 Hz, 2C), 37.5 (, J = 57 Hz, 2C), 30.8 (, J = 4 Hz, 6C), 27.9 (s, 6C), 26.6 (s, 2C), 17.8 (, J = 50, 4 Hz, 1C), 12.3 (, J = 5 Hz, 1C); 31 P{ 1 H} NMR (CDCl 3, 202 MHz) δ: 91.7 (, J = 7 Hz), 69.0 (, J = 7 Hz); 19 F NMR (CDCl 3, 470 MHz) δ: 62.4; Aal. Cal or C 57 H 62 BF 24 NOP 2 P, C, 48.48; H, 4.43; N, ou: C, 48.26; H, 4.59; N, S13

14 (SP-4-4)-({[(i-trt-utylphosphio-κP)mthyl]imthylphosphi oxi-κo}(mthyl)(2,6-imthylpyrii)pallaium){ttrakis[3,5-is(triluoromthyl)phyl] orat} (3): To a solutio o 2 (79 m, 0.20 mmol, 1.0 quiv) a 2,6-lutii (35 µl, 0.30 mmol, 1.5 quiv) i ihloromtha (5.0 ml) was a NaBAr F 4 (180 m, 0.20 mmol, 1.0 quiv) at amit tmpratur a th ratio mixtur was stirr or 22 hours at amit tmpratur. Th th ratio mixtur was iltrat throuh a syri iltr to rmov th orm soium salt a vaporat to rmov th volatil mattrs. Th ru matrial was issolv ito ihloromtha (a. 5.0 ml) aai a rrystalliz rom ihloromtha/hxa to otai th titl prout i 81% (215.3 m, 0.16 mmol) yil. 1 H NMR (CDCl 3, 500 MHz) δ: 7.70 (r, 8H), 7.64 (t, J = 7.8 Hz, 1H), 7.52 (r, 4H), 7.17 (, J = 7.6 Hz, 2H), 2.95 (s, 6H), 2.27 (, J = 9.6, 9.6Hz, 2H), 1.61 (, J = 12.8 Hz, 6H), 1.40 (, J = 15.0 Hz, 18H), 0.60 (, J = 1.5 Hz, 3H); 13 C{ 1 H} NMR (CDCl 3, 126 MHz) δ: (m, 4C), (s, 2C), (s, 1C), (s, 8C), (qq, J = 32, 3 Hz, 8C), (q, J = 272 Hz, 8C), (s, 1C), (s, 1C), (sptt, J = 4 Hz, 4C), 36.4 (, J = 16, 3 Hz, 2C), 29.2 (, J = 5 Hz, 6C), 26.5 (s, 2C), 25.5 (, J = 67, 9 Hz, 1C), 17.8 (, J = 71 Hz, 2C), 10.6 (, J = 4 Hz, 1C); 31 P{ 1 H} NMR (CDCl 3, 202 MHz) δ: 66.7 (, J = 12 Hz), 61.9 (, J = 12 Hz); 19 F NMR (CDCl 3, 470 MHz) δ: 62.4 (s); Aal. Cal or C 51 H 50 BF 24 NOP 2 P, C, 46.12; H, 3.79; N, ou: C, 45.92; H, 3.81; N, S14

15 (SP-4-4)-[(mthyl)[imthyl({is[(1R,2S,5R)-5-mthyl-2-(propa-2-yl)ylohxyl]phosphio-κ P}mthyl)phosphi oxi-κo](2,6-imthylpyrii)pallaium]{ttrakis[3,5-is(triluoromthyl)phyl]orat} (3): To a solutio o 2 (52 m, mmol, 1.0 quiv) a 2,6-lutii (11 µl, mmol, 1.0 quiv) i ihloromtha (2.0 ml) was a NaBAr F 4 2H 2 O (85 m, mmol, 1.0 quiv) at amit tmpratur a th ratio mixtur was stirr or 17 hours at amit tmpratur. Th th ratio mixtur was iltrat throuh a syri iltr to rmov th orm soium salt a vaporat to rmov th volatil mattrs. Th ru matrial was issolv ito ithyl thr (a. 2.0 ml) a th rsulti solutio was a ropwis to th viorously stirri pta solutio to otai th titl prout i 72% (99 m, mmol) yil. 1 H NMR (CDCl 3, 400 MHz) δ: 7.70 (r, 8H), 7.64 (t, J = 7.6 Hz, 1H), 7.52 (s, 4H), 7.18 (, J = 7.2 Hz, 1H), 7.16 (, J = 7.8 Hz, 1H), 4.02 (r, 1H), 3.03 (s, 3H), 2.87 (s, 3H), (m, 1H), (m, 2H), (m, 1H), (m, 2H), (m, 5H), (m, 5H), (m, 13H), (m, 16H), 0.51 (, J = 2.5 Hz, 3H); 13 C{ 1 H} NMR (CDCl 3, 126 MHz) δ: (m, 4C), (s, 1C), (s, 1C), (s, 1C), (s, 8C), (qq, J = 32, 3 Hz, 8C), (q, J = 272 Hz, 8C), (, J = 3 Hz, 1C), (, J = 3 Hz, 1C), (sptt, J = 4 Hz, 4C), 48.3 (, J = 4 Hz, 1C), 43.7 (s, 1C), 40.5 (, J = 19, 3 Hz, 1C), 36.2 (s, 1C), 35.5 (, J = 7 Hz, 1C), 35.2 (, J = 23, 2 Hz, 1C), 34.5 (s, 1C), 34.1 (s, 1C), 33.8 (, J = 12 Hz, 1C), 33.2 (, J = 7 Hz, 1C), 28.7 (, J = 5 Hz, 1C), 28.3 (, J = 10 Hz, 1C), 27.5 (s, 1C), 26.2 (s, 1C), 26.0 (, J = 68, 9 Hz, 1C), 25.2 (s, 1C), 25.2 (, J = 21 Hz, 1C), 22.9 (s, 1C), 22.6 (s, 1C), 22.0 (s, 1C), 21.9 (s, 1C), 18.3 (, J = 71 Hz, 1C), 17.5 (, J = 72, 2 Hz, 1C), 16.8 (s, 1C), 16.5 (s, 1C), 9.7 (, J = 5 Hz, 1C); 31 P{ 1 H} NMR (CDCl 3, 202 MHz) δ: 68.4 (, J = 15 Hz), 29.1 (, J = 15 Hz); 19 F NMR (CDCl 3, 470 MHz) δ: 62.4 (s); Aal. Cal or C 63 H 70 BF 24 NOP 2 P, C, 50.70; H, 4.73; N, ou: C, 50.51; H, 4.83; N, S15

16 1-3. Gral Prour or Polymrizatios A Rprstativ Prour or Ethyl Polymrizatio (Tal 1, try 1) A 50-mL stailss stl autolav was ri i a ov at 120 C, a th allow to ool isi a ry ox. Atr ooli, a aliquot (1.0 ml) o a stok solutio o atalyst 3a (7.5 µmol) i ihloromtha (10 ml) was a ito th autolav. Atr th volatil mattrs wr rmov i vauo, tolu (15 ml) was a. Atr th autolav was sal a har with thyl (3.0 MPa), th ratio mixtur was stirr i a isothrmal hati lok or 1 h at 100 C. Th ratio was quh y aitio o mthaol (a. 20 ml). Th mixtur was iltr a wash with mthaol. Th otai solis wr issolv i hot o-ihloroz, rpripitat y aitio o mthaol (a. 50 ml), iltr, a ri ur vauum or 3 hours at 120 C to aor polythyl (0.70 ). Th molular wiht a polyisprsity wr trmi y siz xlusio hromatoraphy. Th xtt o rahi i th polymr ako was trmi y quatitativ 13 C{ 1 H} NMR sptrosopy. A Prour or Copolymrizatio o Ethyl a Viyl Atat (Tal 2, try 3) A 50 ml stailss stl autolav was ri i a ov at 120 C, a th allow to ool isi a ry ox. Atr ooli, 3 (14.9 m, 10 µmol), tolu (3.0 ml), a viyl atat (12.0 ml) wr a ito th autolav. Atr th autolav was sal a har with thyl (3.0 MPa), th ratio mixtur was stirr i a isothrmal hati lok or 15 h at 80 C. Th ratio was quh y aitio o mthaol (a. 10 ml). Th mixtur was iltr a wash with mthaol. Th otai solis wr issolv i hot o-ihloroz, rpripitat y aitio o mthaol (a. 50 ml), iltr, a ri ur vauum or 3 hours at 120 C to aor poly(thyl-o-viyl atat) (0.38 ). Th molular wiht a polyisprsity wr trmi y siz xlusio hromatoraphy. Th iorporatio ratio o viyl atat a th xtt o rahi i th polymr ako wr trmi y quatitativ 13 C{ 1 H} NMR sptrosopy. A Prour or Copolymrizatio o Ethyl a Butyl Viyl Ethr (Tal 2, try 6) A 50 ml stailss stl autolav was ri i a ov at 120 C, a th allow to ool isi a ry ox. Atr ooli, 3 (15.1 m, 10 µmol), tolu (3.0 ml), a utyl viyl thr (12.0 ml) wr a ito th autolav. Atr th autolav was sal a har with thyl (3.0 MPa), th ratio mixtur was stirr i a isothrmal hati lok or 15 h at 100 C. Th ratio was quh y aitio o mthaol (a. 10 ml). Th solvt was rmov i vauo a th rsulti ummy soli was wash with hot hloroorm y Soxhlt xtratio or 62 hours. Th otai soli was ri ur vauum or 5 hours at 100 C to aor poly(thyl-o-utyl viyl thr) (0.37 ). Th molular wiht a polyisprsity wr trmi y siz xlusio hromatoraphy. Th iorporatio ratio o viyl atat a th xtt o rahi i th polymr ako wr trmi y quatitativ 13 C{ 1 H} NMR sptrosopy. S16

17 Copolymrizatio o Ethyl a Mthyl Arylat i th Prs o Galvioxyl (Tal 2, try 10) A 50 ml stailss stl autolav was ri i a ov at 120 C, a th allow to ool isi a ry ox. Atr ooli, 3 (14.9 m, 10 µmol), alvioxyl (21.0 m, 50 µmol), tolu (3.0 ml), a mthyl arylat (12.0 ml) wr a ito th autolav. Th autolav was th sal, har with thyl (3.0 MPa) a stirr i a isothrmal hati lok at 100 C or 15 h. Th ratio was quh y aitio o mthaol (a. 10 ml). Th mixtur was iltr a wash with mthaol. Th otai solis wr issolv i hot o-ihloroz, rpripitat y aitio o mthaol (a. 50 ml), iltr, a ri ur vauum or 5 hours at 100 C to aor poly(thyl-o-mthyl arylat) (0.47 ). Th molular wiht a polyisprsity wr trmi y siz xlusio hromatoraphy. Th iorporatio ratio o viyl atat a th xtt o rahi i th polymr ako wr trmi y quatitativ 13 C{ 1 H} NMR sptrosopy. S17

18 2. NMR Sptra o Lias a Catalysts Fiur S1. 1 H NMR sptrum o 2a (CDCl 3, 500 MHz) Fiur S2. 13 C{ 1 H} NMR sptrum o 2a (CDCl 3, 126 MHz). S18

19 Fiur S3. 1 H NMR sptrum o 2 (CDCl 3, 500 MHz, 60 C) Fiur S4. 13 C{ 1 H} NMR sptrum o 2 (CDCl 3, 126 MHz, 60 C). S19

20 CHCl Fiur S5. 1 H NMR sptrum o 2 (CDCl 3, 500 MHz) CDCl Fiur S6. 13 C{ 1 H} NMR sptrum o 2 (CDCl 3, 126 MHz). S20

21 Fiur S7. 1 H NMR sptrum o 2 (CDCl 3, 400 MHz) Fiur S8. 13 C{ 1 H} NMR sptrum o 2 (CDCl 3, 126 MHz). S21

22 Fiur S9. 1 H NMR sptrum o 2 (CDCl 3, 500 MHz) Fiur S C{ 1 H} NMR sptrum o 2 (CDCl 3, 126 MHz). S22

23 Fiur S11. 1 H NMR sptrum o 2 (CDCl 3, 500 MHz) Fiur S C{ 1 H} NMR sptrum o 2 (CDCl 3, 126 MHz). S23

24 Fiur S13. 1 H NMR sptrum o 3a (CDCl 3, 500 MHz) Fiur S C{ 1 H} NMR sptrum o 3a (CDCl 3, 126 MHz). S24

25 CHCl Fiur S15. 1 H NMR sptrum o 3 (CDCl 3, 500 MHz) CDCl Fiur S C{ 1 H} NMR sptrum o 3 (CDCl 3, 126 MHz). S25

26 Fiur S17. 1 H NMR sptrum o 3 (CDCl 3, 500 MHz) Fiur S C{ 1 H} NMR sptrum o 3 (CDCl 3, 126 MHz). S26

27 CHCl Fiur S19. 1 H NMR sptrum o 3 (CDCl 3, 500 MHz) CDCl Fiur S C{ 1 H} NMR sptrum o 3 (CDCl 3, 126 MHz). S27

28 Fiur S21. 1 H NMR sptrum o 3 (CDCl 3, 500 MHz) Fiur S C{ 1 H} NMR sptrum o 3 (CDCl 3, 126 MHz). S28

29 CHCl Fiur S23. 1 H NMR sptrum o 3 (CDCl 3, 400 MHz) Fiur S C{ 1 H} NMR sptrum o 3 (CDCl 3, 126 MHz). S29

30 3. NMR Sptra o Polymrs M a h i j k l C 2 H 2 Cl * = uitii ** = artiat CHCl 2 CCl k C 2 Cl 6 j * * ** ** Fiur S25. Quatitativ 13 C NMR sptrum o th polythyl i Tal 1, try 1 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) h i M a j k l + a 1000 M r. (/1000 C) = (all aro) a =1.6 * = uitii ** = artiat h a ** i l * ** Fiur S26. Hih il rio (0 50 ppm) o quatitativ 13 C NMR sptrum o th polythyl i Tal 1, try 1 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C). S30

31 M a C 2 H 2 Cl 4 h k i j l 4.29 k C 2 Cl j CHCl 2 CCl Fiur S27. Quatitativ 13 C NMR sptrum o th polythyl otai i Tal 1, try 2 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) Fiur S28. Hih il rio (0 50 ppm) o quatitativ 13 C NMR sptrum o th polythyl otai i Tal 1, try 2 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C). S31

32 M a C 2 H 2 Cl 4 h i j k l CHCl 2 CCl 3 k C 2 Cl 6 j Fiur S29. Quatitativ 13 C NMR sptrum o th polythyl i Tal 1, try 3 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) M a M r. (/1000 C) = a 1000 (all aro) a h i j k l =3.7 l i h a Fiur S30. Hih il rio (0 50 ppm) o quatitativ 13 C NMR sptrum o th polythyl i Tal 1, try 3 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C). S32

33 Fiur S31. Quatitativ 13 C NMR sptrum o th polythyl otai i Tal 1, try 4 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) a M r. (/1000 C) = a 1000 (all aro) a =9.0 a Fiur S32. Hih il rio (0 50 ppm) o quatitativ 13 C NMR sptrum o th polythyl otai i Tal 1, try 4 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C). S33

34 C 2 H 2 Cl 4 * = uitii ** = artiats CHCl 2 CCl 3 C 2 Cl 6 + uitii ** ** ** ** Fiur S33. Quatitativ 13 C NMR sptrum o th polythyl otai i Tal 1, try 5 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) a a 1000 M r. (/1000 C) = (all aro) a = * = uitii ** = artiats ** a Fiur S34. Hih il rio (0 50 ppm) o quatitativ 13 C NMR sptrum o th polythyl otai i Tal 1, try 5 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C). S34

35 Fiur S35. Quatitativ 13 C NMR sptrum (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) o th polythyl otai i Tal 1, try 6. S35

36 Fiur S36. Quatitativ 13 C NMR sptrum o th thyl/allyl atat opolymr otai i Tal 2, try 1 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) Fiur S37. Hih il rio (0 50 ppm) o quatitativ 13 C NMR sptrum o th thyl/allyl atat opolymr otai i Tal 2, try 1 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C). S36

37 Fiur S38. Quatitativ 13 C NMR sptrum o th thyl/allyl atat opolymr otai i Tal 2, try 2 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) M r. (/1000 C) = * = uitii ** = artiats O a O Iorp. (mol%) = (all aro) = a Fiur S39. Hih il rio (0 50 ppm) o quatitativ 13 C NMR sptrum o th thyl/allyl atat opolymr otai i Tal 2, try 2 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C). S37

38 O O a h OA OA ot osrv OA * = uitii ** = artiat m i o j p k q r l s a r 0.26 o k * ** ** Fiur S40. Quatitativ 13 C NMR sptrum o th thyl/viyl atat opolymr otai i Tal 2, try 3 (1,2,4-trihloroz, 126 MHz, 120 C) Fiur S41. Hih il rio (0 50 ppm) o quatitativ 13 C NMR sptrum o th thyl/viyl atat opolymr otai i Tal 2, try 3 (1,2,4-trihloroz, 126 MHz, 120 C). S38

39 Fiur S42. Quatitativ 13 C NMR sptrum o th thyl/viyl atat opolymr otai i Tal 2, try 4 (1,2,4-trihloroz, 126 MHz, 120 C) O O a OA 2a 100 iorp. (mol%) = (all aro) + 2a 4a = OA h i j k l * = uitii ** = artiat i j * Fiur S43. Hih il rio (10 40 ppm) o quatitativ 13 C NMR sptrum o th thyl/viyl atat opolymr otai i Tal 2, try 4 (1,2,4-trihloroz, 126 MHz, 120 C). S39

40 O a i h h i CHCl 2 CCl C 2 Cl 6 a ** ** Fiur S44. Quatitativ 13 C NMR sptrum o th thyl/utyl viyl thr opolymr otai i Tal 2, try 5 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) i O a i h h i iorp. (mol%) = (all aro) = 0.83 h Fiur S45. Hih il rio (10 40 ppm) o quatitativ 13 C NMR sptrum o th thyl/utyl viyl thr opolymr otai i Tal 2, try 5 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C). S40

41 O a i h h i a Fiur S46. Quatitativ 13 C NMR sptrum o th thyl/utyl viyl thr opolymr otai i Tal 2, try 6 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) i O a i h h i iorp. (mol%) = (all aro) = 1.6 h Fiur S47. Hih il rio (0 50 ppm) o quatitativ 13 C NMR sptrum o th thyl/utyl viyl thr opolymr otai i Tal 2, try 6 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C). S41

42 CHCl 2 CCl w x C 2 Cl 6 ** ** Fiur S48. Quatitativ 13 C NMR sptrum o th thyl/aryloitril opolymr otai i Tal 2, try 7 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) M z aa ot osrv a CN ot osrv p o q ot osrv CN r * = uitii ** = artiat h CN m i k j l ot osrv s u t ot osrv x v w y v * * y ** 2.68 h Fiur S49. Hih il rio (10 40 ppm) o quatitativ 13 C NMR sptrum o th thyl/aryloitril opolymr otai i Tal 2, try 7 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C). S42

43 Fiur S50. Quatitativ 13 C NMR sptrum o th thyl/aryloitril opolymr otai i Tal 2, try 8 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) Fiur S51. Low il rio ( ppm) o quatitativ 13 C NMR sptrum o th thyl/aryloitril opolymr otai i Tal 2, try 8 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C). S43

44 Fiur S52. Hih il rio (10 40 ppm) o quatitativ 13 C NMR sptrum o th thyl/aryloitril opolymr otai i Tal 2, try 8 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) Fiur S53. Quatitativ 13 C NMR sptrum o th thyl/mthyl arylat opolymr otai i Tal 2, try 9 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C). S44

45 Fiur S54. Hih il rio (10 55 ppm) o quatitativ 13 C NMR sptrum o th thyl/ mthyl arylat opolymr otai i Tal 2, try 9 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) O a OM h i * = uitii ** = artiat 1.00 CHCl 2 CCl ** ** Fiur S55. Quatitativ 13 C NMR sptrum o th thyl/mthyl arylat opolymr otai i Tal 2, try 10 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C). S45

46 iorp. (mol%) = (all aro) O a OM = 1.6 h i * = uitii ** = artiat a ** Fiur S56. Hih il rio (0 60 ppm) o quatitativ 13 C NMR sptrum o th thyl/ mthyl arylat opolymr otai i Tal 2, try 10 (1,1,2,2-ttrahlorotha, 126 MHz, 120 C) i + a+j+m polymr trmial Fiur S57. 1 H NMR o th thyl/allyl atat opolymr otai i Tal 2, try 16 (1,1,2,2-ttrahlorotha- 2, 126 MHz, 120 C). S46

47 k +o h l Fiur S58. Low-il rio ( ppm) o 1 H NMR o th thyl/allyl atat opolymr otai i Tal 2, try 16 (1,1,2,2-ttrahlorotha- 2, 126 MHz, 120 C). O O OA a OA OA h i j k OA OA OA iorp. = l o p m p o (++2+i+h/2) 100 (++)/4+4.95/6+(++2+i+h/2) a+i+l+o =2.7mol% k m j+p + h polymr trmial Fiur S59. 1 H NMR o th thyl/viyl atat opolymr otai i Tal 2, try 17 (1,1,2,2-ttrahlorotha- 2, 126 MHz, 120 C). S47

48 Fiur S60. Quatitativ 13 C NMR sptrum o th thyl/aryloitril opolymr otai i Tal 2, try 18 (1,1,2,2-ttrahlorotha- 2, 126 MHz, 120 C) M z aa a CN o p q CN r * = uitii ** = artiat i h CN m k j l v s w t x y u t u CHCl 2CCl 3 p(e) p(z) w x m a C 2Cl 6 r(z) r(e) q(e) q(z) Fiur S61. Low il rio ( ppm) o quatitativ 13 C NMR sptrum o th thyl/aryloitril opolymr otai i Tal 2, try 18 (1,1,2,2-ttrahlorotha- 2,126 MHz, 120 C). S48

49 M z aa a CN o p q CN r + h s t u + * = uitii ** = artiat i j CN m k l v w x y j s +v aa o(z) o(e) +i+ k z l r h Fiur S62. Hih il rio (10 40 ppm) o quatitativ 13 C NMR sptrum o th thyl/ aryloitril opolymr otai i Tal 2, try 18 (1,1,2,2-ttrahlorotha- 2, 126 MHz, 120 C). ** A a++++++h+d E A: =10.65 G F B H C +i Fiur S63. 1 H NMR o th thyl/mthyl arylat opolymr otai i Tal 2, try 19 (1,1,2,2-ttrahlorotha- 2, 126 MHz, 120 C). S49

50 a++++++h+f C O B O A F E D E F A C +i k +o l I j+m p+e Fiur S64. 1 H NMR o th thyl/mthyl mtharylat opolymr otai i Tal 2, try 20 (1,1,2,2-ttrahlorotha- 2, 126 MHz, 120 C) a++++++h+f+l(1h) A C C O B O A +i F E D E F H k H +o l I G K L (1H) J j+m p+e Fiur S65. 1 H NMR o th thyl/mthyl mtharylat opolymr otai i Tal 2, try 21 (1,1,2,2-ttrahlorotha- 2, 126 MHz, 120 C). S50

51 a++++++h+f+l(1h) C A C O B O A I +i F E D E F L (1H) J H k +o+h l G K j+m p+e Fiur S66. 1 H NMR o th thyl/mthyl mtharylat opolymr otai i Tal 2, try 22 (1,1,2,2-ttrahlorotha- 2, 126 MHz, 120 C). S51