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RSC CHEMCOMM TEMPLATE (MAC)

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CREATED USING THE RSC CHEMCOMM TEMPLATE - SEE HTTP://WWW.RSC.ORG/IS/JOURNALS/TEMPLATES/TEMPLATES.HTM FOR DETAILS ...

    CREATED USING THE RSC CHEMCOMM TEMPLATE - SEE HTTP://WWW.RSC.ORG/IS/JOURNALS/TEMPLATES/TEMPLATES.HTM FOR DETAILS

    Supplementary Material (ESI) for Chemical Communications This journal is ? The Royal Society of Chemistry 2002

Synthesis

    HHHHbafeHHgcN

    OHNHHdhH1HiH2

    H3

    HH54

    NMR Assignments

N-phenyl 3-(9-anthracenyl)-2-hydroxybenzyl imine (2A) [N-Phenyl anthracenyl-salicylaldimine]: To a slurry of anthracenyl-salicylaldehyde A (0.50 g, 1.676 mmoles) suspended in 10 mls of ethanol was added aniline (0.50 mls, excess) and a drop of formic

    acid. The slurry was stirred overnight. The pale yellow product collected by filtration and washed with ethanol before being dried in a ovacuum oven at 60C. Yield 0.48 g (77%). 1H -NMR 13.65(s, 1H, OH), 8.822(s, 1H, CHN), 8.549(s, 1H, H), 8.079(d, 2H J = 7.7 Hz, Anth-H), 7.719(d, 2H J = 7.93 Hz, Anth- aH), 7.636(dd, 1H J = 7.7 & 1.7 Hz, Ph-H), 7.35 7.51(brm, Anth-H and Ph), 7.24(brm, Ph Ph-H), 7.194(t, 1H J = 7.6 Hz, Hc). 131C{H}-NMR 162.40, 159.56, 148.11, 139.92, 136.41, 132.36, 131.58, 130.44, 129.44, 128.63, 127.07, 126.49, 125.60, 125.13, 121.17, 119.47, 119.02.

    Ir(KBr disk) 3500br, 3048w, 3026w, 2700br, 1943w, 1614s, 1576s, 1491m, 1479m, 1440s, 1409m, 1354m, 1313w, 1295m, 1266m,

    1218w, 1198s, 1169sh, 1162m, 1148w, 1077m, 1021m, 1013m, 981m, 967w, 909m, 884m, 857m, 846m, 792s, 778w, 770m, 755s, 736s, 694s, 687sh, 636m, 621w, 590m, 562m, 533m, 509w, 494w, 472w. -MS(CI-ve) (m/z) 373(M-H 100%)

    CHNO (373.46): Calc. C 86.84, H 5.13, N 3.75; Found C 86.71, H 4.99, N 3.69. 2719

    N-isopropyl 3-(9-anthracenyl)-2-hydroxybenzyaldimine (25A) [N-isopropyl anthracenyl-salicylaldimine]: Yield 0.36 g (63%). 1H -NMR 14.017(s, 1H, OH), 8.527(s, 1H, H5), 8.515(s, 1H, CHN), 8.065(brd, 2H J = 7.7 Hz, Anth-H), 7.699(brd, 2H J = 7.7 Hz, iAnth-H), 7.52-7.34(brm, 6H, H2&3 and Hb&c), 7.105(t, 1H J = 7.5 Hz, Hc), 3.583(sept, 1H J = 6.4 Hz, Pr-CH), 1.245(d, 6H J = 6.4 iHz, Pr-Me). 131C{H}-NMR 162.06, 159.83, 135.27, 132.81, 131.56, 131.11, 130.42, 128.53, 126.84, 126.61, 126.16(?), 125.43, 125.02, 118.98, 118.21,59.84, 24.13.

    Ir(KBr disk) 3450br, 3049m, 2995w, 2969m, 2955m, 2926w, 2867m, 2856m, ?2700br, 1946w, 1926w, 1626s, 1603s, 1483w, 1446s, 1408m, 1383m, 1357m, 1311m, 1293m, 1267m, 1218m, 1148s, 1073w, 1019w, 1013w, 976w, 953w, 912w, 891m, 871w, 857m, 846m, 794m, 786w, 754s, 736s, 681w, 636m, 589w, 557w, 527w, 492w. -MS(CI-ve) (m/z) 339(M-H, 100%)

    CHNO (339.44): Calc. C 84.92, H 6.24, N 4.13; Found C 84.88, H 6.23, N 4.01. 2421

    N-(2-pyridyl)-methyl 3-(9-anthracenyl)-2-hydroxybenzyl imine (32A) [N-(2-pyridyl)-methyl anthracenyl-salicylaldimine]: To a slurry of anthracenyl-salicylaldehyde A (0.50 g, 1.676 mmoles) suspended in 10 mls of ethanol was added 2-aminomethylpyridine (0.50 mls, excess) and a drop of formic acid. The slurry was stirred at reflux overnight then cooled to RT. The yellow product was collected by ofiltration and washed with ethanol before being dried in a vacuum oven at 60C. Yield 0.44 g 67.5(%). 1H -NMR (400 MHz, CDCl) 4.935(s, 2H, H), 7.142(2 cooincident t’s, 2H J ? 7.5 Hz, H & H), 7.291(d, 1H J = 7.8 Hz, H), 7.34- 3echf7.41(m, 3H, H& H), 7.452(t, 2H J = 7.8 Hz, H), 7.536(dd, 1H J 7.7 & 1.6 Hz, H), 7.574(dt, 1H J = 7.7 & 1.8 Hz, H), 7.681(d, 2H J 2 d3bg= 8.8 Hz, H), 8.054(d, 2H J = 8.5 Hz, H), 8.521(s, 1H, H) overlapping with 8.531(d, 1H J = 8.6 Hz, H), 8.719(s, 1H, H), 13.577(s, 14ai51H, OH). 131C{H} NMR (100 MHz, CDCl) 65.1, 118.7, 119.0, 122.2, 122.4, 125.1, 125.5, 126.5, 126.6, 127.0, 128.6, 130.4, 131.5, 131.7, 132.5, 3135.8, 136.8, 149.4, 157.7, 159.4, 166.7.

    Ir(KBr disk) 3054w, 3028sh, 2886sh, 2961w, 2886w, 1947w, 1914w, 1803w, 1638s, 1591s, 1571m, 1478w, 1436s, 1451s, 1343w, 1311w, 1290m, 1269m, 1210w, 1145m, 1058w, 998w, 861w, 746s, 640s, 606m, 504m, 472m. --MS(CI -ve) (m/z) 388 (M-H 75%), 296 (M-CHPy 100%). 2CHNO (388.47): Calc. C 83.48, H 5.19; Found C, H. 27202

    N-(2-pyridyl)-methyl 3-(9-triptycyl)-2-hydroxybenzylimine (32D) [N-(2-pyridyl)-methyl triptycyl-salicylaldimine]: To a slurry of triptycyl-salicylaldehyde D (0.50 g, 1.33 mmoles) suspended in 10 mls of ethanol was added 2-aminomethylpyridine (0.50 mls, excess) and a drop of formic acid. The slurry was stirred at reflux overnight then cooled to RT. The yellow product was collected by filtration oand washed with ethanol before being dried in a vacuum oven at 60C. Yield 0.48 g 77.7(%). 1H-NMR (400 MHz, CDCl) ;;J = 7.7 & 1.3 Hz, H), 6.976(dt, 3H, J = 7.3 & 321.0 Hz,

    H), 7.167(dd, 1H J = 7.4 & 1.3 Hz, H), 7.223(t, 1H J = 7.7 Hz, H), 7.255-7.294(m, 4H, H & H), 7.412(dd, 3H J = 7.2 & 1.1 Hz, H), 3hc1f47.564(dd, 1H J = 7.5 & 1.4 Hz, H), 7.606(dt, 1H J = 7.7 & 1.8 Hz, H), 8.511(dd, 1H J = 7.9 & 1.4 Hz, H), 8.552(brd, 1H J = 4.5 Hz, bgdH), 8.722(s, 1H, H), 13.989(s, 1H, OH). ia131C{H}-NMR (100 MHz, CDCl) 55.2, 59.1, 65.0, 118.1, 119.8, 122.3, 122.4, 123.4, 124.3, 124.5, 124.8, 125.0, 131.9, 135.2, 136.9, 3145.5, 146.2, 149.3, 157.6, 161.3, 166.9. Ir(KBr disk) 3450br, 3074w, 3050m, 3006m, 2922w, 2878m, ? 2640br, 1924w, 1623s, 1589s, 1571sh, 1475m, 1447s, 1409m, 1381m,

    CREATED USING THE RSC CHEMCOMM TEMPLATE - SEE HTTP://WWW.RSC.ORG/IS/JOURNALS/TEMPLATES/TEMPLATES.HTM FOR DETAILS

    1358m, 1324m, 1295m, 1264m, 1231m, 1219m, 1168w, 1145w, 1099w, 1080m, 1038m, 1013m, 994w, 911w, 892m, 846s, 795m, 784sh, 778m, 771m, 751s, 742s, 684w, 650sh, 642m, 615w, 581w, 557w, 519sh, 511w, 481m. +-MS(CI-ve) (m/z) 464 (M 85%), 372 (M-CHPy 100%). 2CHNO (464.57): Calc. C 85.32, H 5.21, N 6.03; Found C 85.36, H 5.15, N 5.95. 33242

    (N-(2-pyridyl)-methyl triptycyl-salicylaldimino)chromium(III) dichloride (3d): Ligand 32D (0.50 g, 1.105 mmoles) and p-tolylCrCl(thf) (0.41 g, 1.105 mmoles) were reacted by dissolving in 20 mls of thf. A brown solid precipitated almost immediately. 23The slurry was stirred for 1 hour and the solids recovered by filtration and washed with 2 x 10 mls of thf. Yield 0.586 g 90.5(%).

    Ir(KBr disk) 3435br, 3067m, 3005m, 2958m, 2887w, ?2500br, 1950w, 1913w, 1630s, 1599s, 1571sh, 1473sh, 1453s, 1435s, 1377w, 1330w, 1288m, 1267m, 1147m, 1124w, 1100w, 1083w, 1050m, 1036m, 1019sh, 998w, 944w, 914w, 902w, 859w, 842w, 790w, 757s, 746s, 669w, 646s, 606m, 587w, 563w, 504m, 471w.? +++FAB-MS (m/z) 1137(LCrCl, 15%), 550(M-Cl, 100%), 513(LCr, 80%) 223CHNOCrCl (586.47): Calc. C 67.59, H 3.95, N 4.78; Found C 67.51, H 3.97, N 4.71. 332322

    Catalysis Activated Catalyst Solution Formation: A mixture of the required ligand (0.030 mmoles) and p-tolylCrCl(thf) (12.9 mg, 0.030 32mmoles) were dissolved in 10 mls of dry degassed toluene and allowed to stir for 5 minutes, the initial yellow colour turned a brown

    yellow. The solvent was removed under vacuum and the brown residue slurried in 26.2 mls of dry degassed toluene. The pro-catalyst was activated by the addition of MAO (3.8 mls, 1.6 M, 6.0 mmoles) and the slightly darker solution allowed to stir for 5 minutes.

Schlenk Test: A 5 ml aliquot (5 moles) of the activated catalyst solution was transferred to a Schlenk containing 95 mls of dry degassed toluene. The vessel was sealed and evacuated. The vessel was placed under 1 Bar of ethylene pressure and allowed to react

    for 1 hour. The solution was deactivated by depressurising and addition of 100 mls of methanol containing 2 mls of dilute HCl. The opolymer was recovered by filtration, washed with methanol and dried in a vacuum oven at 60C overnight. The combined filtrates were collected and the solvent removed on a Rot-Vap. The residue was dissolved in 50 mls of toluene and filtered through 2 cm of alumina

    and the alumina was washed with 2 x 10 mls of toluene. To the combined filtrates was added 1 ml of nonane and the sample submitted

    for GC analysis. The combined catalytic data for tests using ligands 6-9 are collected in Table 1.

    Large Reactor: An automated 1 litre Buchi reactor was prepared with 400 mls of isobutane at the required temperature and pressure of

    ethylene. The reactor was scavenged with 1.25 mls of 1.6 M MAO (2.0 mmoles) solution in toluene. A 5 ml aliquot (5 moles) of the activated catalyst solution was transferred to the large reactor and the ethylene uptake monitored for the catalyst run. After 60 minutes othe isobutane was vented and the polymer collected and dried in a vacuum oven at 60C overnight.

     High Throughput Screen Procedure: The ligand (5 mol) was mixed with a solution of p-(tolyl)CrCl(THF) (5 mol in 1.5 mL 23toluene), and MAO was added (0.5 mL of a 1.8M solution in toluene, 180 eq.) The solution was then stirred under an ethylene atmosphere (1 bar) for 15 min; the activity was determined by polymer yield.

CREATED USING THE RSC CHEMCOMM TEMPLATE - SEE HTTP://WWW.RSC.ORG/IS/JOURNALS/TEMPLATES/TEMPLATES.HTM FOR DETAILS

CH3PhONH2NH2HC3CHHC33114274053NHN2PhPhONHCHNH322NHFF2FNH2CH3FHCCH21528415433FFNHCHCHNH2332F2NHCH3HN2NHCH23CH3CHCH3HCN2S3ONHHN31629425522NHCHC33SOOHN2NH2NH2CH3CHCHO33NN4173043ClHONHCNH3NH22CHCH33HNCH23NHO22NHSNH25183144ClHNHCCH33OCH3NH2HN2NNH26193245NCH32NHCHFHC33NHN2ONHBr2HCN37203346FOFNHNH2FHC32HN2FNHNHF22N8213447OCH3NHF2HC3HC3CH3HNCHHCNH2332HNCHHNOCH92235482323OCH3

HNNH22NHCH32O10233649ONNNHNSCH23CH3HC3NH2NH2OHC112437503NH2NH2HC3CH3BrCHHC33HN12253851N2NH2CHHN32NH2CH3NHN2FONCH3ClH13263952FNNFHNHN22ONHCHF23

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