Organometallics
Communication
(5) For some recent reviews, see: (a) Puerta, M. C.; Valerga, P.
Coord. Chem. Rev. 1999, 193−195, 977. (b) Metal Vinylidenes and
Allenylidenes in Catalysis: From Reactivity to Applications in Synthesis;
Bruneau, C., Dixneuf, P., Eds.; Wiley-VCH: Weinheim, Germany,
2008. (c) Selegue, J. P. Coord. Chem. Rev. 2004, 248, 1543.
(6) (a) Ikeda, Y.; Yamaguchi, T.; Kanao, K.; Kimura, K.; Kamimura,
S.; Mutoh, Y.; Tanabe, Y.; Ishii, Y. J. Am. Chem. Soc. 2008, 130, 16856.
(b) Otsuka, M.; Tsuchida, N.; Ikeda, Y.; Kimura, Y.; Mutoh, Y.; Ishii,
Y.; Takano, K. J. Am. Chem. Soc. 2012, 134, 17746. (c) Ikeda, Y.;
Mutoh, Y.; Imai, K.; Tsuchida, N.; Takano, K.; Ishii, Y. Organometallics
2013, 32, 4353.
Scheme 2. Proposed Mechanism for Formation of Allene
Complexes
(7) Hughes, D. L.; Pombeiro, A. J. L.; Pickett, C. J.; Richards, R. L. J.
Chem. Soc. Chem. Commun. 1984, 992.
(8) Werner, H.; Schwab, P.; Mahr, N.; Wolf, J. Chem. Ber. 1992, 125,
2641.
(9) Casey, C. P.; Brady, J. T. Organometallics 1998, 17, 4620.
(10) Frank-Neumann, M.; Brion, F. Angew. Chem., Int. Ed. Engl.
1979, 18, 688.
(11) Coughlan, S. C.; Yang, G. K. J. Organomet. Chem. 1993, 450,
151.
broad temperature range, which allowed the thermodynamic
parameters to be determined. Addition of external base did not
have any impact on the observed rate of isomerization, seeming
to preclude a catalytic role being played by trace quantities of
acid.
(12) Wen, T. B.; Zhou, Z. Y.; Lau, C.-P.; Jia, G. Organometallics 2000,
19, 3466.
(13) Findlater, M.; Cartwright-Sykes, A.; White, P. S.; Schauer, C. K.;
Brookhart, M. J. Am. Chem. Soc. 2011, 133, 12274.
(14) For related in situ generation of 14-electron systems see:
(a) Gottker-Schnetmann, I.; White, P. S.; Brookhart, M. J. Am. Chem.
Soc. 2004, 126, 1804. (b) Gottker-Schnetmann, I.; White, P. S.;
Brookhart, M. Organometallics 2004, 23, 1766. (c) Gottker-
Schnetmann, I.; Brookhart, M. J. Am. Chem. Soc. 2004, 126, 9330.
(15) See the Supporting Information for details of the synthesis and
characterization of metal complexes and calculations pertaining to rate
and thermodynamic parameters.
(16) For reports of related transition-metal π-allene complexes, see
the following. (a) Au: Brown, T. J.; Sugie, A.; Dickens, M. G.;
Widenhoefer, R. A. Organometallics 2010, 29, 4207. (b) Re: Pu, J.;
Peng, T.-S.; Arif, A. M.; Gladysz, J. A. Organometallics 1992, 11, 3232.
(c) Fe: Omrcen, T.; Conti, N. J.; Jones, W. M. Organometallics 1991,
10, 913. (d) W: Chacon, S. T.; Chisholm, M. C.; Folting, K.;
Huffman, J. C.; Hampden-Smith, M. J. Organometallics 1991, 10, 3722.
(e) Ir: Lundquist, E. G.; Folting, K.; Streib, W. E.; Huffman, J. C.;
Eisenstein, O.; Caulton, K. G. J. Am. Chem. Soc. 1990, 112, 855. (f) Pt:
Winchester, W. R.; Jones, W. M. Organometallics 1985, 4, 2228. (g)
Pd: Okamoto, K.; Kai, Y.; Yasuoka, N.; Kasai, N. J. Organomet. Chem.
1974, 65, 427.
ASSOCIATED CONTENT
* Supporting Information
■
S
Text, figures, and a CIF file giving X-ray crystallographic data
and complete synthetic and characterization details of all metal
complexes. This material is available free of charge via the
AUTHOR INFORMATION
Corresponding Author
■
Author Contributions
All authors have given approval to the final version of the
manuscript.
Notes
The authors declare no competing financial interest.
(17) Findlater, M.; Bernskoetter, W. H.; Brookhart, M. J. Am. Chem.
Soc. 2010, 132, 4534.
(18) Silvestre, A.; Hoffmann, R. Helv. Chim. Acta 1985, 68, 1461.
(19) Biswas, S.; Huang, Z.; Choliy, Y.; Wang, D. Y.; Brookhart, M.;
Krogh-Jesperson, K.; Goldman, A. S. J. Am. Chem. Soc. 2012, 134,
13276.
ACKNOWLEDGMENTS
■
Dedicated to Professor Maurice Brookhart on the occasion of
his 70th birthday. M.F. gratefully acknowledges Texas Tech
University for startup funds. The authors thank the National
Science Foundation for funding the purchase of NMR
instrumentation (Grant No. CHE-1048553) used in this
project.
(20) Gotzig, J.; Otto, H.; Werner, H. J. Organomet. Chem. 1985, 287,
247.
REFERENCES
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