Organometallics
Article
by NMR spectroscopy before exposure to UV light. No reaction was
observed. The reaction mixture was then exposed to 254 nm light
overnight. NMR spectroscopic analysis after that showed disappear-
ance of the starting material and formation of complex 4 (ca. 50%) and
(e) Wang, D.; Wurst, K.; Knolle, W.; Decker, U.; Prager, L.; Naumov,
S.; Buchmeiser, M. R. Angew. Chem., Int. Ed. 2008, 47, 3267. (f) Wang,
D.; Wurst, K.; Buchmeiser, M. R. Chem.Eur. J. 2010, 16, 12928.
(g) Vidavsky, Y.; Lemcoff, N. G. Beilstein J. Org. Chem. 2010, 6, 1106 ,
and references therein. (h) Buchmeiser, M. R.; Wang, D. Latent
Photoactivatable Precatalysts for Metathesis Polymerization. U.S.
Patent 0,003,905, January 6, 2011.
1
4
vinylphosphonium salt [CH CHPCy ][OTf]. Formation of
2
3
1
poly(isopropoxystyrene) was also observed by H NMR spectroscopy.
ASSOCIATED CONTENT
Supporting Information
Further experimental details, kinetic plots, and selected NMR
(5) For examples of photoinduced RCM, see: (a) Picquet, M.;
Bruneau, C.; Dixneuf, P. H. Chem. Commun. 1998, 2249. (b) Furstner,
̈
A.; Ackermann, L. Chem. Commun. 1999, 95. (c) Ben-Asuly, A.;
Aharoni, A.; Diesendruck, C. E.; Vidavsky, Y.; Goldberg, I.; Straub, B.
F.; Lemcoff, N. G. Organometallics 2009, 28, 4652. (d) Keitz, B. K.;
Grubbs, R. H. J. Am. Chem. Soc. 2009, 131, 2038.
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(
6) Carlson, R. G.; Gile, M. A.; Heppert, J. A.; Mason, M. H.; Powell,
D. R.; van der Velde, D.; Vilain, J. M. J. Am. Chem. Soc. 2002, 124,
580.
7) Romero, P. E.; Piers, W. E. Transition Metal Carbene Complexes
AUTHOR INFORMATION
Corresponding Author
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1
(
Containing a Cationic Substituent as Catalysts of Olefin Metathesis
Reactions. International Patent Appl. WO 2005/121158 A1, December
Notes
2
2, 2005.
The authors declare no competing financial interest.
(8) (a) Romero, P. E.; Piers, W. E.; McDonald, R. Angew. Chem., Int.
Ed. 2004, 43, 6161. (b) Dubberley, S. R.; Romero, P. E.; Piers, W. E.;
McDonald, R.; Parvez, M. Inorg. Chim. Acta 2006, 359, 2658. (c) van
der Eide, E. F.; Romero, P. E.; Piers, W. E. J. Am. Chem. Soc. 2008, 130,
ACKNOWLEDGMENTS
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This work was supported by the Natural Sciences and
Engineering Research Council of Canada through a Discovery
Grant (W.E.P.) and a CGS-D Award (E.M.L.) and Intel
Corporation (A.Y.K.). W.E.P. acknowledges the Canada
Council of the Arts for a Killam Research Fellowship (2012-
4
485. (d) Leitao, E. M.; Dubberley, S. R.; Piers, W. E.; Wu, Q.;
McDonald, R. Chem.Eur. J. 2008, 14, 11565. (e) Leitao, E. M.; van
Der Eide, E. F.; Romero, P. E.; Piers, W. E.; McDonald, R. J. Am.
Chem. Soc. 2010, 132, 2784. (f) van der Eide, E. F.; Piers, W. E. Nat.
Chem. 2010, 2, 571.
1
4). Materia Inc. of Pasadena, CA, is acknowledged for
(9) Odian, G. Principles of Polymerization, 4th ed.; Wiley-Interscience:
Hoboken, NJ, 2004.
providing samples of Grubbs Generation 2 olefin metathesis
catalyst employed in the preparation of 1.
(
(
10) See Supporting Information for details.
11) The process by which triphenylsulfonium PAGs release protons
under UV irradiation is complex and produces several organic
byproducts; see: (a) Araki, S.; Ito, H.; Butsugan, Y. J. Org. Chem.
REFERENCES
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(
1) (a) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413.
1
988, 53, 1833. (b) Dektar, J. L.; Hacker, N. P. J. Am. Chem. Soc. 1990,
(
b) Fu
̈
rstner, A. Angew. Chem., Int. Ed. 2000, 39, 3013. (c) Trnka, T.
1
12, 6004. For clarity, this chemistry is not depicted in the schemes
M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18.
herein, but for a more complete picture the reader is directed to these
references.
(
2) (a) Ito, H.; Willson, C. G. Applications of Photoinitiators to the
Design of Resists for Semiconductor Manufacturing. In Polymers in
Electronics; Davidson, T., Ed.; ACS Symposium Series, Vol. 242; ACS
Publications: Washington, DC, 1984; pp 11−23. (b) Ung, T.; Hejl, A.;
Grubbs, R. H.; Schrodi, Y. Organometallics 2004, 23, 5399. (c) Slugovc,
C.; Burtscher, D.; Stelzar, F.; Mereiter, K. Organometallics 2005, 24,
255. (d) Harris, R. F.; Ricci, M. J.; Farrer, R. A.; Praino, J.; Miller, S.
J.; Saleh, B. E. A.; Teich, M. C.; Fourkas, J. T. Adv. Mater. 2005, 17, 39.
e) Hejl, A.; Day, M. W.; Grubbs, R. H. Organometallics 2006, 25,
149. (f) Toohey, K. S.; Sottos, N. R.; Lewis, J. A.; Moore, J. S.; White,
(12) (a) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J.;
Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791. (b) Garber, S. B.;
Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000,
1
(
22, 8168.
13) For an example of UV-induced polymerization of styrenes, see:
Deng, J.-P.; Yang, W.-T.; Ranby, B. Macromol. Rapid Commun. 2001,
2, 535.
14) (a) [CH C(H)PCy ][Br]: Rabinowitz, R.; Henry, A. C.;
2
̊
2
(
(
6
2
3
Mercus, R. J. Polymer Sci: A 1965, 3, 2055. (b) [CH C(H)PCy ]
2
3
S. R. Nat. Mater. 2007, 6, 581. (g) Monsaert, S.; Ledoux, N.; Drozdzak,
R.; Verpoort, F. J. Polym. Sci. A: Polym. Chem. 2010, 48, 302.
[
BF ]: Esteruelas, M. A.; Lahoz, F. J.; Martin, M.; Martinez, A.; Oro,
4
L. A.; Puerta, M. C.; Valerga, P. J. Organomet. Chem. 1999, 577, 265.
c) Jung, S.; Brandt, J. W.; Werner, H. Dalton Trans. 2004, 375. (d)
CH C(H)PCy ][B(C F ) ]: Romero, P. E.; Piers, W. E. J. Am.
(
2
(
h) Samec, J. S. M.; Keitz, B. K.; Grubbs, R. H. J. Organomet. Chem.
010, 695, 1831.
3) For example: (a) Ben-Asuly, A.; Tzur, E.; Diesendruck, C. E.;
Sigalov, M.; Goldberg, I.; Lemcoff, N. G. Organometallics 2008, 27,
11. (b) Szadkowska, A.; Grela, K. Curr. Org. Chem. 2008, 12, 1631.
c) Monsaert, S.; Lozanno Vila, A.; Drozdzak, R.; Van Der Voort, P.;
(
[
2
3
6 5 4
Chem. Soc. 2005, 127, 5032.
15) Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.;
Timmers, F. J. Organometallics 1996, 15, 1518.
(
8
(
Verpoort, F. Chem. Soc. Rev. 2009, 38, 3360. (d) Szadkowska, A.;
Gstrein, X.; Burtscher, D.; Jarzembska, K.; Wozniak, K.; Slugovc, C.;
Grela, K. Organometallics 2010, 29, 117. (e) Yu, Z.; Rogan, Y.;
Khosravi, E.; Musa, O. M.; Hobson, L.; Batsanov, A. S. J. Organomet.
Chem. 2011, 696, 1591. (f) Diesendruck, C. E.; Iliashevsky, O.; Ben-
Asuly, A.; Goldberg, I.; Lemcoff, N. D. Macromol. Symp. 2010, 293, 33.
(
g) Diesendruck, C. E.; Vidavsky, Y.; Ben-Asuly, A.; Lemcoff, N. G. J.
Polym. Sci., A: Polym. Chem. 2009, 47, 4209.
4) For examples of photoinduced ROMP, see: (a) Van Der Schaaf,
P. A.; Hafner, A.; Muhlebach, A. Angew. Chem., Int. Ed. Engl. 1996, 35,
845. (b) Delaude, L.; Demonceau, A.; Noels, A. F. Chem. Commun.
001, 986. (c) Delaude, L.; Szypa, M.; Demonceau, A.; Noels, A. F.
(
̈
1
2
Adv. Synth. Catal. 2002, 344, 749. (d) Zhang, Y.; Wang, D.; Lonnecke,
P.; Scherzer, T.; Buchmeiser, M. R. Macromol. Symp. 2006, 236, 30.
5
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dx.doi.org/10.1021/om3005965 | Organometallics 2012, 31, 5634−5637