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Branched polymers via ROMP of termimers

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(1)http://doc.rero.ch. Published in Macromolecular Rapid Communications 37(6): 532–538, 2016 which should be cited to refer to this work. Supporting Information.        CH3. H 3C N. H 3C. O. N CH3. H 3C. CH3. O Cl. N. N. CH3. N. Ru Ph. Cl. O. O. N. Br. Br. exo-N-cyclohexyl-norbornene-2,3-dicarboximide 5 (CyNI). exo-N-methylnorbornene imide 6 (MNI). 3rd. generation initiator Grubbs' ((H 2IMes)(3-Br-Py) 2(Cl) 2Ru=CHPh = C3).   $%#&%&#$!!"!& $- /. Figure SI-1. Reaction of C1 with 2 (3 eq). The graph shows the residual carbene signal at 20.05 ppm in time resolved 1H NMR spectroscopy in methylene chloride-d2, 400 MHz at room temperature. The Integrals were referenced to the residual solvent signal of methylene chloride.. 6.

(2) http://doc.rero.ch. Figure SI-2. Reaction of C1 with 2 (3 eq). Top left, right and bottom: The graphs show the time resolved 1H NMR spectra corresponding to Figure SI-1 in methylene chloride-d2, 400 MHz at room temperature. Different sections of the same NMR spectra are shown.. 7.

(3) http://doc.rero.ch. 7.23. 7.93. 7.27. 8.09 8.07. 7.26. 7.35 7.31. 7.24. 7.43 7.42. 7.40. 7.33. 7.33. G1CYNIE4SBE_002000FID.ESP. 8.5. 8.0. 7.5. 7.0 Chemical Shift (ppm). 6.5. 6.0. 5.5. Figure SI-3: 1H NMR analysis (in chloroform-d1, 400 MHz) of active ester terminated poly(CyNI). Aromatic signals referring to the focal benzylidene unit (also referred to as a styryl unit) and the terminal succinimidyl 4-ethenylenebenzoate unit (7.2-8.2 ppm) transferred during the termination of the propagating ruthenium catalyst C1 with 2..  

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(5)  00 $$$"%#&$!( %& %! *%# % "!*2* 3$"$2%#) $'#%#&!#!%%!#%! +%! 3/ 8.

(6) http://doc.rero.ch. . Figure SI-5: MALDI-ToF-MS analysis of the singly-branched poly(PNI). The bimodal molecular weight distribution corresponds well to the observed GPC results. Figures SI-5 - SI-7 show expanded and isotopically resolved peaks from this graph.. . 9.

(7) http://doc.rero.ch. Figure SI-6: MALDI-ToF-MS analysis showing the recorded isotopic pattern for poly(PNI) terminated with ethyl vinyl ether, and the isotopic pattern for [C8H96N8O16+Ag]+. (m/z) calculated for [C8H96N8O16+Ag]+, 1627.6; found, 1627.6.. . :.

(8) http://doc.rero.ch Figure SI-7: MALDI-ToF-MS analysis showing the recorded isotopic pattern for poly(PNI). terminated. with. termimer. 4,. and. the. isotopic. pattern. for. [C111H122N10O18+Ag]+ (u). (m/z) calculated for [C111H122N10O18+Ag]+, 2005.8; found, 2005.9.. . ;.

(9) http://doc.rero.ch Figure SI-8: MALDI-ToF-MS analysis showing the recorded isotopic pattern for poly(PNI). terminated. with. termimer. 4,. and. the. isotopic. pattern. for. [C169H185N15O29+Ag]+ (u). (m/z) calculated for [C169H185N15O29+Ag]+, 2995.3; found, 2995.4.. . <.

(10) http://doc.rero.ch. Figure SI-9: Top: Model reaction investigated over time by 1H-NMR spectroscopy. Bottom: Time resolved 1H NMR spectra (methylene chloride-d2, 400 MHz). An isomeric mixture of tributyl-(2-ethoxyethenyl)stannane (cis/trans = 75/25) was reacted with a 3-fold excess of catalyst C1 over 21 hours (front to back). The signals of the cis (yellow) and trans (red) isomer were integrated with respect to TMS as internal standard. The experiment indicates high substrate selectivity towards the cisvinyl ether.. =.

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Figure

Figure SI-1. Reaction of C1 with 2 (3 eq). The graph shows the residual carbene signal at 20.05 ppm in time resolved 1 H NMR spectroscopy in methylene chloride-d 2 , 400 MHz at room temperature
Figure SI-3: 1 H NMR analysis (in chloroform-d 1 , 400 MHz) of active ester terminated poly(CyNI)
Figure SI-5: MALDI-ToF-MS analysis of the singly-branched poly(PNI). The
Figure SI-8: MALDI-ToF-MS analysis showing the recorded isotopic pattern for

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