Organometallics
COMMUNICATION
therefore, the reactivity observed here is characteristic of the
aminoacetylene moiety bound to the redox-responsive tetrairon
core. Transformation would be driven by thermodynamically
Widenhoefer, R. A.; Hallenbeck, S. L.; Hayashi, R. K. Inorg. Chem. 1994,
33, 2639.
1
3
(10) (a) Fortune, J.; Manning, A. R.; Stephens, F. S. J. Chem. Soc.,
Chem. Commun. 1983, 1071. (b) Cullen, E. P.; Fortune, J.; Manning,
A. R.; McArdle, P.; Cunningham, D.; Stephenes, F. S. Organometallics
favorable formation of the μ -CO moiety, although the reaction
3
mechanism concerning the nucleophilic substitution is not yet
certain.
1
990, 9, 1443. (c) Manning, A. R.; O'Dwyer, L.; McArdle, P. A.;
Cunningham, D. J. Organomet. Chem. 1994, 474, 173.
11) Filippou, A. C.; Lungwitz, B.; Kociok-K €o hn, G. Eur. J. Inorg.
Chem. 1999, 1905.
12) For M transition-metal clusters (n > 2), there have been very
(
(
n
limited examples of aminoalkyne-coordinated compounds to date. The
reactivity of these clusters remains largely unknown. Adams, R. D.;
Chem, G.; Tanner, J. T.; Yin, J. Organometallics 1990, 9, 1240.
(13) Clusters [4](PF
6 2 6
) and [5](PF ) are stable toward moisture
even in solution.
’
ASSOCIATED CONTENT
S
Supporting Information. Experimental procedures,
b
spectroscopic data, and a CIF file for [5](PF ). This material is
6
available free of charge via the Internet at http://pubs.acs.org.
’
AUTHOR INFORMATION
Corresponding Author
*E-mail: mokazaki@cc.hirosaki-u.ac.jp.
’
ACKNOWLEDGMENT
This work was supported by the Collaborative Research
Program of Institute for Chemical Research, Kyoto University
grant 2010-6). M.O. acknowledges the funding program for
Next Generation World-Leading Researchers.
(
’
REFERENCES
(1) (a) Shriver, D. F.; Kaesz, H. D.; Adams, R. D. The Chemistry of
Metal Cluster Complexes; VCH: New York, 1990. (b) Fehlner, T. P.;
Halet, J.-F.; Saillard, J.-Y. Molecular Clusters: A Bridge to Solid-State
Chemistry; Cambridge University Press: Cambridge, 2007.
(2) (a) Okazaki, M.; Ohtani, T.; Ogino, H. J. Am. Chem. Soc. 2004,
126, 4104. (b) Okazaki, M.; Ohtani, T.; Takano, M.; Ogino, H.
Organometallics 2004, 23, 4055. (c) Okazaki, M.; Takano, M.; Ozawa,
F. J. Am. Chem. Soc. 2009, 131, 1684.
(3) (a) Montauzon, D. D.; Mathieu, R. J. Organomet. Chem. 1983,
252, C83. (b) Dahan, F.; Mathieu, R. J. Chem. Soc., Chem. Commun.
1984, 432. (c) Yeh, W.-Y.; Shapley, J. R. J. Organomet. Chem. 1986,
315, C29. (d) Nuel, D.; Dahan, F.; Mathieu, R. Organometallics 1985,
4, 1436. (e) Edwin, J.; Geiger, W. E.; Salzer, A.; Ruppli, U.; Rheingold,
A. L. J. Am. Chem. Soc. 1987, 109, 7893. (f) Suades, J.; Dahan, F.;
Mathieu, R. Organometallics 1988, 7, 47. (g) Geiger, W. E.; Salzer, A.;
Edwin, J.; von Philipsborn, W.; Piantini, U.; Rheingold, A. L. J. Am.
Chem. Soc. 1990, 112, 7113. (h) Inagaki, A.; Takaya, Y.; Takemori, T.;
Suzuki, H.; Tanaka, M.; Haga, M. J. Am. Chem. Soc. 1997, 119, 625.
(
i) Takao, T.; Moriya, M.; Suzuki, H. Organometallics 2007, 26, 1349.
4) Okazaki, M.; Ohtani, T.; Inomata, S.; Tagaki, N.; Ogino, H.
J. Am. Chem. Soc. 1998, 120, 9135.
5) (a) Takano, M.; Okazaki, M.; Tobita, H. J. Am. Chem. Soc. 2004,
26, 9190. (b) Okazaki, M.; Takano, M.; Yoshimura, K. J. Organomet.
Chem. 2005, 690, 5318.
(
(
1
(
(
(
6) Mingos, D. M. P. Acc. Chem. Res. 1984, 17, 311.
7) Chen, J.; Wang, R. Coord. Chem. Rev. 2002, 231, 109.
8) Okazaki, M.; Ohtani, T.; Takano, M.; Ogino, H. Inorg. Chem.
2
002, 41, 6726.
9) (a) Rashidi, M.; Kristof, E.; Vittal, J. J.; Puddephatt, R. J. Inorg.
(
Chem. 1994, 33, 1497. (b) Ratliff, K. S.; Broeker, G. K.; Fanwick, P. E.;
Kubiak, C. P. Angew. Chem., Int. Ed. Engl. 1990, 29, 395. (c) Casey, C. P.;
3
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dx.doi.org/10.1021/om200493b |Organometallics 2011, 30, 3487–3489