Macromolecules
Article
Hawker, C. J., Sakamoto, J., Eds.; Wiley-VCH: Weinheim, 2012; Vol.
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(11) Kandre, R.; Feldman, K.; Meijer, H. E. H.; Smith, P.; Schluter,
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A. D. Angew. Chem., Int. Ed. 2007, 46, 4956−4959.
(12) A and B refer to bromide and boronate groups, respectively.
Note that the monomer structure intrinsically preset their mole ratio
to be 1:1.
(13) For a high molecular weight hyperbranched PMP by SPC, see:
Xue, Z.; Finke, A. D.; Moore, J. S. Macromolecules 2010, 43, 9277−
9282.
(14) For PMPs with rather low molecular weights by SPC using AA/
BB monomers, see: (a) Iwasaki, T.; Kohinaka, Y.; Nishide, H. Org.
Lett. 2005, 7, 755−758. (b) Liu, J.; Pei, Q. Macromolecules 2010, 43,
9608−9612.
(15) (a) Wegner, G. Macromol. Chem. Phys. 2003, 204, 347−357.
(b) Wegner, G. Macromol. Symp. 2003, 201, 1−9.
(16) End-capping is often aimed at for removing halo and boron
functional groups which possibly remain at the chain ends of SPC
products and could be detrimental for materials properties. However,
the end-group situation before and after the end-capping has been
little understood. See refs 4c and d.
Figure 11. MALDI-TOF mass spectra obtained from SPCs using (a)
Pd(dba)2 (0.01 equiv for 1a), (b) Pd(OAc)2 (0.01 equiv), and (c)
Pd(OAc)2 (0.1 equiv) as palladium source for catalyst. The signals
marked with arrows are the SPC products indicative of the occurrence
of the homocoupling presumably caused by the action of Pd(II).
ASSOCIATED CONTENT
■
S
* Supporting Information
All experimental procedures including NMR and HR-MS data,
GPC elution curves, and a MALDI-TOF mass spectrum of SPC
using Pd(OAc)2 (0.1 equiv) as palladium source. This material
(17) Kissel, P.; Breitler, S.; Reinmuller, V.; Lanz, P.; Federer, L.;
̈
AUTHOR INFORMATION
■
Schluter, A. D.; Sakamoto, J. Eur. J. Org. Chem. 2009, 2953−2955.
̈
Corresponding Author
*Fax +41 44 633 1398; Tel +41 44 633 4221; e-mail
(18) “p-Tol” is an abbreviation of p-tolyl.
(19) Jakob, S.; Moreno, A.; Zhang, X.; Bertschi, L.; Smith, P.;
Schluter, A. D.; Sakamoto, J. Macromolecules 2010, 43, 7916−7918.
̈
(20) Yashima and co-workers reported a similar bimodal GPC curve
from the products of Yamamoto polycondensation with a m-phenylene
dibromide monomer carrying an oligo(ethylene oxide) side group. See
ref 9.
(21) Flessner, T.; Doye, S. J. Prakt. Chem. 1999, 341, 186−190.
(22) (a) Kong, K.-C.; Cheng, C.-H. J. Am. Chem. Soc. 1991, 113,
6313−6315. (b) Morita, D. K.; Stille, J. K.; Norton, J. R. J. Am. Chem.
Soc. 1995, 117, 8576−8581. (c) Goodson, F. E.; Wallow, T. I.; Novak,
B. M. J. Am. Chem. Soc. 1997, 119, 12441−12453.
(23) When Pd[P(p-Tol)3]3 is used as catalyst for SPC, ligand
scrambling leads to products whose chain ends are capped with either
p-Tol or P(p-Tol)2. The latter can sometimes be oxidized to P(O)
(p-Tol)2 during subsequent work-up. See: Frahn, J.; Karakaya, B.;
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The authors thank Prof. N. Miyaura (Hokkaido University) for
discussion and useful advice, Dr. T. Schweizer (ETH Zurich)
for his help in GPC analysis, and Mr. F. Wisser (ETH Zurich)
for his help in synthesis. Financial support by the Swiss
National Science Foundation (200020_126451) is gratefully
acknowledged.
REFERENCES
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(26) Hydration (protonation) or hydroxylation accompanies
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(3) For initial papers of SPC, see: (a) Rehahn, M.; Schluter, A. D.;
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dx.doi.org/10.1021/ma300888j | Macromolecules 2012, 45, 5418−5426