Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2010 Jan 1;29(15):3413-3417.
doi: 10.1021/om100468q.

Chain- and Regioselective Ethylene and Styrene Dimerization Reactions Catalyzed by a Well-Defined Cationic Ruthenium-Hydride Complex: New Insights on the Styrene Dimerization Mechanism

Do W Lee  1 , Chae S Yi
Affiliations

Chain- and Regioselective Ethylene and Styrene Dimerization Reactions Catalyzed by a Well-Defined Cationic Ruthenium-Hydride Complex: New Insights on the Styrene Dimerization Mechanism

Do W Lee et al. Organometallics. .

Abstract

The cationic ruthenium-hydride complex [(eta(6)-C(6)H(6))(PCy(3))(CO)RuH](+)BF(4) (-) was found to be a highly regioselective catalyst for the ethylene dimerization reaction to give 2-butene products (TOF = 1910 h(-1), >95% selectivity for 2-butenes). The dimerization of styrene exclusively produced the head-to-tail dimer (E)-PhCH(CH(3))CH=CHPh at an initial turnover rate of 2300 h(-1). A rapid and extensive H/D exchange between the vinyl hydrogens of styrene-d(8) and 4-methoxystyrene was observed within 10 min without forming the dimer products at room temperature. The inverse deuterium isotope effect of k(H)/k(D) = 0.77+/-0.10 was measured from the first order plots on the dimerization reaction of styrene and styrene-d(8) in chlorobenzene at 70 degrees C. The pronounced carbon isotope effect on both vinyl carbons of styrene as measured by using Singleton's method ((13)C(recovered)/(13)C(virgin) at C(1) = 1.096 and C(2) = 1.042) indicates that the C-C bond formation is the rate-limiting step for the dimerization reaction. The Eyring plot of the dimerization of styrene in the temperature range of 50-90 degrees C led to DeltaH(double dagger) = 3.3(6) kcal/mol and DeltaS(double dagger) = -35.5(7) e.u. An electrophilic addition mechanism has been proposed for the dimerization of styrene.

PubMed Disclaimer

Figures

Figure 1
Figure 1
Plot of ln[ethylene] vs time at 50 °C.
Figure 2
Figure 2
First Order Plots of the Dimerization of Styrene (∎) and Styrene-d8 (●) at 70 °C.
Figure 3
Figure 3
Eyring Plot for the Styrene Dimerization.
Scheme 1
Scheme 1
Proposed Mechanism of the Styrene Dimerization Reaction.
Scheme 2
Scheme 2
See this image and copyright information in PMC

Similar articles

See all similar articles

Cited by

See all "Cited by" articles

References

    1. Reviews: Pillai SM, Ravindranathan M, Sivaram S. Chem. Rev. 1986;86:353–399.. Skupinska J. Chem. Rev. 1991;91:613–648.. Mecking S. Coord. Chem. Rev. 2000;203:325–351.. Speiser F, Braunstein P, Saussine L. Acc. Chem. Res. 2005;38:784–793..

    1. Olivier-Bourbigou H, Saussine L. In: Applied Homogeneous Catalysis with Organometallic Compounds. Cornils B, Herrmann WA, editors. Volume 1. Wiley-VCH; Weinheim: 2002.
    2. Keim W. Angew. Chem., Int. Ed. 1990;29:235–244.
    1. Keim W, Behr A, Röper M. In: Comprehensive Organometallic Chemistry. Wilkinson G, Stone FGA, Abel EW, editors. Volume 12. Pergamon Press; New York: 1982.
    2. Datta S, Fischer MB, Wreford SS. J. Organomet. Chem. 1980;188:353–366.
    3. Schrock R, McLain S, Sancho J. Pure Appl. Chem. 1980;52:729–732.
    4. Andes C, Harkins SB, Murtuza S, Oyler K, Sen A. J. Am. Chem. Soc. 2001;123:7423–7424. - PubMed
    5. Yu Z-X, Houk KN. Angew. Chem., Int. Ed. 2003;42:808–811. - PubMed
    1. Bhalla G, Oxgaard J, Goddard WA, III, Periana RA. Organometallics. 2005;24:5499–5502.
    2. Tsuchimoto T, Kamiyama S, Negoro R, Shirakawa E, Kawakami Y. Chem. Commun. 2003:852–853. - PubMed

    1. Recent selected examples with Cr catalysts. Dixon JT, Green MJ, Hess FM, Morgan DH. J. Organomet. Chem. 2004;689:3641–3668.. McGuinness DS, Wasserscheid P, Keim W, Morgan D, Dixon JT, Bollmann A, Maumela H, Hess F, Englert U. J. Am. Chem. Soc. 2003;125:5272–5273.. Blann K, Bollmann A, Dixon JT, Hess FM, Killian E, Maumela H, Morgan DH, Neveling A, Otto S, Overett MJ. Chem. Commun. 2005:620–621.. Agapie T, Labinger JA, Bercaw JE. J. Am. Chem. Soc. 2007;129:14281–14295.. Arteaga-Müller R, Tsurugi H, Saito T, Yanagawa M, Oda S, Mashima K. J. Am. Chem. Soc. 2009;131:5370–5371..

    2. Examples with Ti catalysts: Deckers PJW, Hessen B, Teuben JH. Angew. Chem., Int. Ed. 2001;40:2516–2519.. Otten E, Batinas AA, Meetsma A, Hessen B. J. Am. Chem. Soc. 2009;131:5298–5312.. Suzuki Y, Kinoshita S, Shibahara A, Ishii S, Kawamura K, Inoue Y, Fujita T. Organometallics. 2010;29:2394–2396..

LinkOut - more resources