Macromolecules, Vol. 37, No. 11, 2004
Communications to the Editor 3975
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byproduct alkyne under open driven conditions to form
the corresponding PAEs in excellent yields. Polymer 5
and 6 are defect-free according to 13C NMR spectroscopy.
The protocol for alkyne metathesis we described herein
represents an alternative and efficient approach to
prepare high molecular weight PAEs.
(10) Weiss, K.; Michel, A.; Auth, E.-M.; Bunz, U. H. F.; Mangel,
T.; Mu¨llen, L. Angew. Chem., Int. Ed. Engl. 1997, 36, 506-
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Ack n ow led gm en t. This material is based upon
work supported by the U.S. Department of Energy,
Division of Materials Sciences, under Award DEFG02-
91ER45439, through the Frederick Seitz Materials
Research Laboratory at the University of Illinois at
Urbana-Champaign.
(11) Acyclic diyne metathesis is similar to acyclic diene metath-
esis (ADMET) which was pioneered by Wagener and Bon-
cella. See: (a) Lindmarkhamberg, M.; Wagener, K. B.
Macromolecules 1987, 20, 2949-2951. (b) Wagener, K. B.;
Boncella, J . M.; Nell, J . G.; Duttweiler, R. P.; Hillmyer, M.
A. Makromol. Chem. 1990, 191, 365-374.
Su p p or tin g In for m a tion Ava ila ble: Experimental pro-
cedures, characterization data for 3-6, and absorption and
emission spectra of PTEs 6. This material is available free of
(12) Mortreux, A.; Blanchard, M. Chem. Commun. 1974, 786-
787.
(13) Pschirer, N. G.; Bunz, U. H. F. Tetrahedron Lett. 1999, 40,
2481-2484. (b) Fu¨rstner, A.; Mathes, C. Org. Lett. 2001, 3,
221-223 and ref 9b.
(14) Tamao, K.; Sumitani, K.; Kiso, Y.; Zembayashi, M.; Fijioka,
A.; Kodama, S. I.; Nakajima, I.; Minato, A.; Kumada, M.
Bull. Chem. Soc. J pn. 1976, 49, 1958.
Refer en ces a n d Notes
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(18) General procedure for the polymerization: Under argon, to
a solution of dialkynyl-substituted monomer (0.15 mmol) in
1,2,4-trichlorobenzene (0.8 mL) was added a solution of
molybdenum triamide (2) (4.0 mg, 0.006 mmol) and p-
nitrophenol (2.5 mg, 0.018 mmol) in 1,2,4-trichlorobenzene
(0.8 mL). The resulting mixture was stirred for 22 h at 30
°C under vacuum (1 mmHg). Any precipitated polymer was
dissolved by the addition of CH2Cl2. Addition of methanol
causes the polymeric product to precipitate. The solid is
filtered and vacuum-dried, giving yields as summarized in
Table 1 and Supporting Information.
(19) During the metathesis of 3a ,b, it was observed that PPEs
precipitated out of the solution. Therefore, the poor solubility
of 5a ,b in 1,2,4-trichlorobenzene at 30 °C likely explains the
formation of low molecular weight PPEs in both cases.
(20) In small molecule model reactions, the butynyl groups were
superior for reasons previously discussed (ref 1b). However,
for the polymerizations, the propynyl groups were superior.
(21) In alkyne metathesis the only side reaction is alkyne
polymerization through the “ring expansion” mechanism (ref
1b). Polymerization of alkynes by a tungsten carbyne
catalyst was reported before. See: (a) Weiss, K.; Goller, R.;
Lo¨ssel, G. J . Mol. Catal. 1988, 46, 267-275. (b) Bunz, U.
H. F.; Kloppenburg, L. Angew. Chem., Int. Ed. 1999, 38,
478-481. (c) Katz, T. J .; Ho, T, H.; Shih, N. Y.; Ying, Y. C.;
Stuart, V. I. W. J . Am. Chem. Soc. 1984, 106, 2659-2668.
(22) Sluch, M. I.; Godt, A.; Bunz, U. H. F.; Berg, M. A. J . Am.
Chem. Soc. 2001, 123, 6447-6448. (b) Halkyard, C. E.;
Rampey, M. E.; Kloppenburg, L.; Studer-Martinez, S. L.;
Bunz, U. H. F. Macromolecules 1998, 31, 8655-8659.
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