Nanocluster Size-Control and "Magic Number" Investigations. Experimental Tests of the "Living-Metal Polymer" Concept and of Mechanism-Based Size-Control Predictions Leading to the Syntheses of Iridium (0) Nanoclusters Centering about Four Sequential Magic Numbers

Chemistry of Materials

Volumn 9, Issue 12, 1997, Pages 3083-3095

  Watzky, Murielle A ^a   Finke, Richard G ^a  

^a Department of Environmental and Radiological Health Sciences   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000910089     PISSN: 08974756     EISSN: None     Source Type: Journal    
DOI: 10.1021/cm9704387     Document Type: Article

References (139)

1. Lead reviews on nanoclusters: (a) Physics and Chemistry of Small Clusters; Jena, P., Rao, B. K., Khanna, S. N., Eds.; Plenum Press, New York, 1987. (b) Andres, R. P.; Averback, R. S.; Brown, W. L.; Brus, L. E.; Goddard, W. A.; Kaldor, A.; Louie, S. G.; Moscovits, M.; Peercy, P. S.; Riley, S. J.; Siegel, R. W.; Spaepen, F.; Wang, Y. J. Mater. Res. 1989, 4, 704 (a Panel Report from the United States Department of Energy, Council on Materials Science on "Research Opportunities on Clusters and Cluster-assembled Materials"). (c) Thomas, J. M. Pure Appl. Chem. 1988, 60, 1517. (d) Henglein, A. Chem. Rev. 1989, 89, 1861. (e) A superb series of papers, complete with a record of the insightful comments by the experts attending the conference, is available in: Faraday Discuss. 1991, 92, 1-300. (f) Bradley, J. S. In Clusters and Colloids. From Theory to Applications; Schmidt, G., Ed.; VCH Publishers: New York, 1994; pp 459-544. (g) Schmid, G. In Aspects of Homogeneous Catalysis; Ugo, R., Ed.; Kluwer: Dordrecht, 1990; Vol. 7, Chapter 1. (h) Henglein, A. J. Chem. Phys. 1993, 97, 5457. (i) Belloni, J. Curr. Opin. Colloid Interface Sci. 1996, 1, 184. (j) A list of more than 80 lead references is compiled in: Bönnemann, K.; Braun, G.; Brijoux, W.; Brinkmann, R.; Schulze Tilling, A., Seevogel, K.; Siepen, K. J. Organo. Met. Chem. 1996, 520, 143.
2. Lead reviews on nanoclusters: (a) Physics and Chemistry of Small Clusters; Jena, P., Rao, B. K., Khanna, S. N., Eds.; Plenum Press, New York, 1987. (b) Andres, R. P.; Averback, R. S.; Brown, W. L.; Brus, L. E.; Goddard, W. A.; Kaldor, A.; Louie, S. G.; Moscovits, M.; Peercy, P. S.; Riley, S. J.; Siegel, R. W.; Spaepen, F.; Wang, Y. J. Mater. Res. 1989, 4, 704 (a Panel Report from the United States Department of Energy, Council on Materials Science on "Research Opportunities on Clusters and Cluster-assembled Materials"). (c) Thomas, J. M. Pure Appl. Chem. 1988, 60, 1517. (d) Henglein, A. Chem. Rev. 1989, 89, 1861. (e) A superb series of papers, complete with a record of the insightful comments by the experts attending the conference, is available in: Faraday Discuss. 1991, 92, 1-300. (f) Bradley, J. S. In Clusters and Colloids. From Theory to Applications; Schmidt, G., Ed.; VCH Publishers: New York, 1994; pp 459-544. (g) Schmid, G. In Aspects of Homogeneous Catalysis; Ugo, R., Ed.; Kluwer: Dordrecht, 1990; Vol. 7, Chapter 1. (h) Henglein, A. J. Chem. Phys. 1993, 97, 5457. (i) Belloni, J. Curr. Opin. Colloid Interface Sci. 1996, 1, 184. (j) A list of more than 80 lead references is compiled in: Bönnemann, K.; Braun, G.; Brijoux, W.; Brinkmann, R.; Schulze Tilling, A., Seevogel, K.; Siepen, K. J. Organo. Met. Chem. 1996, 520, 143.
3. Lead reviews on nanoclusters: (a) Physics and Chemistry of Small Clusters; Jena, P., Rao, B. K., Khanna, S. N., Eds.; Plenum Press, New York, 1987. (b) Andres, R. P.; Averback, R. S.; Brown, W. L.; Brus, L. E.; Goddard, W. A.; Kaldor, A.; Louie, S. G.; Moscovits, M.; Peercy, P. S.; Riley, S. J.; Siegel, R. W.; Spaepen, F.; Wang, Y. J. Mater. Res. 1989, 4, 704 (a Panel Report from the United States Department of Energy, Council on Materials Science on "Research Opportunities on Clusters and Cluster-assembled Materials"). (c) Thomas, J. M. Pure Appl. Chem. 1988, 60, 1517. (d) Henglein, A. Chem. Rev. 1989, 89, 1861. (e) A superb series of papers, complete with a record of the insightful comments by the experts attending the conference, is available in: Faraday Discuss. 1991, 92, 1-300. (f) Bradley, J. S. In Clusters and Colloids. From Theory to Applications; Schmidt, G., Ed.; VCH Publishers: New York, 1994; pp 459-544. (g) Schmid, G. In Aspects of Homogeneous Catalysis; Ugo, R., Ed.; Kluwer: Dordrecht, 1990; Vol. 7, Chapter 1. (h) Henglein, A. J. Chem. Phys. 1993, 97, 5457. (i) Belloni, J. Curr. Opin. Colloid Interface Sci. 1996, 1, 184. (j) A list of more than 80 lead references is compiled in: Bönnemann, K.; Braun, G.; Brijoux, W.; Brinkmann, R.; Schulze Tilling, A., Seevogel, K.; Siepen, K. J. Organo. Met. Chem. 1996, 520, 143.
4. Lead reviews on nanoclusters: (a) Physics and Chemistry of Small Clusters; Jena, P., Rao, B. K., Khanna, S. N., Eds.; Plenum Press, New York, 1987. (b) Andres, R. P.; Averback, R. S.; Brown, W. L.; Brus, L. E.; Goddard, W. A.; Kaldor, A.; Louie, S. G.; Moscovits, M.; Peercy, P. S.; Riley, S. J.; Siegel, R. W.; Spaepen, F.; Wang, Y. J. Mater. Res. 1989, 4, 704 (a Panel Report from the United States Department of Energy, Council on Materials Science on "Research Opportunities on Clusters and Cluster-assembled Materials"). (c) Thomas, J. M. Pure Appl. Chem. 1988, 60, 1517. (d) Henglein, A. Chem. Rev. 1989, 89, 1861. (e) A superb series of papers, complete with a record of the insightful comments by the experts attending the conference, is available in: Faraday Discuss. 1991, 92, 1-300. (f) Bradley, J. S. In Clusters and Colloids. From Theory to Applications; Schmidt, G., Ed.; VCH Publishers: New York, 1994; pp 459-544. (g) Schmid, G. In Aspects of Homogeneous Catalysis; Ugo, R., Ed.; Kluwer: Dordrecht, 1990; Vol. 7, Chapter 1. (h) Henglein, A. J. Chem. Phys. 1993, 97, 5457. (i) Belloni, J. Curr. Opin. Colloid Interface Sci. 1996, 1, 184. (j) A list of more than 80 lead references is compiled in: Bönnemann, K.; Braun, G.; Brijoux, W.; Brinkmann, R.; Schulze Tilling, A., Seevogel, K.; Siepen, K. J. Organo. Met. Chem. 1996, 520, 143.
5. Lead reviews on nanoclusters: (a) Physics and Chemistry of Small Clusters; Jena, P., Rao, B. K., Khanna, S. N., Eds.; Plenum Press, New York, 1987. (b) Andres, R. P.; Averback, R. S.; Brown, W. L.; Brus, L. E.; Goddard, W. A.; Kaldor, A.; Louie, S. G.; Moscovits, M.; Peercy, P. S.; Riley, S. J.; Siegel, R. W.; Spaepen, F.; Wang, Y. J. Mater. Res. 1989, 4, 704 (a Panel Report from the United States Department of Energy, Council on Materials Science on "Research Opportunities on Clusters and Cluster-assembled Materials"). (c) Thomas, J. M. Pure Appl. Chem. 1988, 60, 1517. (d) Henglein, A. Chem. Rev. 1989, 89, 1861. (e) A superb series of papers, complete with a record of the insightful comments by the experts attending the conference, is available in: Faraday Discuss. 1991, 92, 1-300. (f) Bradley, J. S. In Clusters and Colloids. From Theory to Applications; Schmidt, G., Ed.; VCH Publishers: New York, 1994; pp 459-544. (g) Schmid, G. In Aspects of Homogeneous Catalysis; Ugo, R., Ed.; Kluwer: Dordrecht, 1990; Vol. 7, Chapter 1. (h) Henglein, A. J. Chem. Phys. 1993, 97, 5457. (i) Belloni, J. Curr. Opin. Colloid Interface Sci. 1996, 1, 184. (j) A list of more than 80 lead references is compiled in: Bönnemann, K.; Braun, G.; Brijoux, W.; Brinkmann, R.; Schulze Tilling, A., Seevogel, K.; Siepen, K. J. Organo. Met. Chem. 1996, 520, 143.
6. Lead reviews on nanoclusters: (a) Physics and Chemistry of Small Clusters; Jena, P., Rao, B. K., Khanna, S. N., Eds.; Plenum Press, New York, 1987. (b) Andres, R. P.; Averback, R. S.; Brown, W. L.; Brus, L. E.; Goddard, W. A.; Kaldor, A.; Louie, S. G.; Moscovits, M.; Peercy, P. S.; Riley, S. J.; Siegel, R. W.; Spaepen, F.; Wang, Y. J. Mater. Res. 1989, 4, 704 (a Panel Report from the United States Department of Energy, Council on Materials Science on "Research Opportunities on Clusters and Cluster-assembled Materials"). (c) Thomas, J. M. Pure Appl. Chem. 1988, 60, 1517. (d) Henglein, A. Chem. Rev. 1989, 89, 1861. (e) A superb series of papers, complete with a record of the insightful comments by the experts attending the conference, is available in: Faraday Discuss. 1991, 92, 1-300. (f) Bradley, J. S. In Clusters and Colloids. From Theory to Applications; Schmidt, G., Ed.; VCH Publishers: New York, 1994; pp 459-544. (g) Schmid, G. In Aspects of Homogeneous Catalysis; Ugo, R., Ed.; Kluwer: Dordrecht, 1990; Vol. 7, Chapter 1. (h) Henglein, A. J. Chem. Phys. 1993, 97, 5457. (i) Belloni, J. Curr. Opin. Colloid Interface Sci. 1996, 1, 184. (j) A list of more than 80 lead references is compiled in: Bönnemann, K.; Braun, G.; Brijoux, W.; Brinkmann, R.; Schulze Tilling, A., Seevogel, K.; Siepen, K. J. Organo. Met. Chem. 1996, 520, 143.
7. Lead reviews on nanoclusters: (a) Physics and Chemistry of Small Clusters; Jena, P., Rao, B. K., Khanna, S. N., Eds.; Plenum Press, New York, 1987. (b) Andres, R. P.; Averback, R. S.; Brown, W. L.; Brus, L. E.; Goddard, W. A.; Kaldor, A.; Louie, S. G.; Moscovits, M.; Peercy, P. S.; Riley, S. J.; Siegel, R. W.; Spaepen, F.; Wang, Y. J. Mater. Res. 1989, 4, 704 (a Panel Report from the United States Department of Energy, Council on Materials Science on "Research Opportunities on Clusters and Cluster-assembled Materials"). (c) Thomas, J. M. Pure Appl. Chem. 1988, 60, 1517. (d) Henglein, A. Chem. Rev. 1989, 89, 1861. (e) A superb series of papers, complete with a record of the insightful comments by the experts attending the conference, is available in: Faraday Discuss. 1991, 92, 1-300. (f) Bradley, J. S. In Clusters and Colloids. From Theory to Applications; Schmidt, G., Ed.; VCH Publishers: New York, 1994; pp 459-544. (g) Schmid, G. In Aspects of Homogeneous Catalysis; Ugo, R., Ed.; Kluwer: Dordrecht, 1990; Vol. 7, Chapter 1. (h) Henglein, A. J. Chem. Phys. 1993, 97, 5457. (i) Belloni, J. Curr. Opin. Colloid Interface Sci. 1996, 1, 184. (j) A list of more than 80 lead references is compiled in: Bönnemann, K.; Braun, G.; Brijoux, W.; Brinkmann, R.; Schulze Tilling, A., Seevogel, K.; Siepen, K. J. Organo. Met. Chem. 1996, 520, 143.
8. Lead reviews on nanoclusters: (a) Physics and Chemistry of Small Clusters; Jena, P., Rao, B. K., Khanna, S. N., Eds.; Plenum Press, New York, 1987. (b) Andres, R. P.; Averback, R. S.; Brown, W. L.; Brus, L. E.; Goddard, W. A.; Kaldor, A.; Louie, S. G.; Moscovits, M.; Peercy, P. S.; Riley, S. J.; Siegel, R. W.; Spaepen, F.; Wang, Y. J. Mater. Res. 1989, 4, 704 (a Panel Report from the United States Department of Energy, Council on Materials Science on "Research Opportunities on Clusters and Cluster-assembled Materials"). (c) Thomas, J. M. Pure Appl. Chem. 1988, 60, 1517. (d) Henglein, A. Chem. Rev. 1989, 89, 1861. (e) A superb series of papers, complete with a record of the insightful comments by the experts attending the conference, is available in: Faraday Discuss. 1991, 92, 1-300. (f) Bradley, J. S. In Clusters and Colloids. From Theory to Applications; Schmidt, G., Ed.; VCH Publishers: New York, 1994; pp 459-544. (g) Schmid, G. In Aspects of Homogeneous Catalysis; Ugo, R., Ed.; Kluwer: Dordrecht, 1990; Vol. 7, Chapter 1. (h) Henglein, A. J. Chem. Phys. 1993, 97, 5457. (i) Belloni, J. Curr. Opin. Colloid Interface Sci. 1996, 1, 184. (j) A list of more than 80 lead references is compiled in: Bönnemann, K.; Braun, G.; Brijoux, W.; Brinkmann, R.; Schulze Tilling, A., Seevogel, K.; Siepen, K. J. Organo. Met. Chem. 1996, 520, 143.
9. Lead reviews on nanoclusters: (a) Physics and Chemistry of Small Clusters; Jena, P., Rao, B. K., Khanna, S. N., Eds.; Plenum Press, New York, 1987. (b) Andres, R. P.; Averback, R. S.; Brown, W. L.; Brus, L. E.; Goddard, W. A.; Kaldor, A.; Louie, S. G.; Moscovits, M.; Peercy, P. S.; Riley, S. J.; Siegel, R. W.; Spaepen, F.; Wang, Y. J. Mater. Res. 1989, 4, 704 (a Panel Report from the United States Department of Energy, Council on Materials Science on "Research Opportunities on Clusters and Cluster-assembled Materials"). (c) Thomas, J. M. Pure Appl. Chem. 1988, 60, 1517. (d) Henglein, A. Chem. Rev. 1989, 89, 1861. (e) A superb series of papers, complete with a record of the insightful comments by the experts attending the conference, is available in: Faraday Discuss. 1991, 92, 1-300. (f) Bradley, J. S. In Clusters and Colloids. From Theory to Applications; Schmidt, G., Ed.; VCH Publishers: New York, 1994; pp 459-544. (g) Schmid, G. In Aspects of Homogeneous Catalysis; Ugo, R., Ed.; Kluwer: Dordrecht, 1990; Vol. 7, Chapter 1. (h) Henglein, A. J. Chem. Phys. 1993, 97, 5457. (i) Belloni, J. Curr. Opin. Colloid Interface Sci. 1996, 1, 184. (j) A list of more than 80 lead references is compiled in: Bönnemann, K.; Braun, G.; Brijoux, W.; Brinkmann, R.; Schulze Tilling, A., Seevogel, K.; Siepen, K. J. Organo. Met. Chem. 1996, 520, 143.
10. Lead reviews on nanoclusters: (a) Physics and Chemistry of Small Clusters; Jena, P., Rao, B. K., Khanna, S. N., Eds.; Plenum Press, New York, 1987. (b) Andres, R. P.; Averback, R. S.; Brown, W. L.; Brus, L. E.; Goddard, W. A.; Kaldor, A.; Louie, S. G.; Moscovits, M.; Peercy, P. S.; Riley, S. J.; Siegel, R. W.; Spaepen, F.; Wang, Y. J. Mater. Res. 1989, 4, 704 (a Panel Report from the United States Department of Energy, Council on Materials Science on "Research Opportunities on Clusters and Cluster-assembled Materials"). (c) Thomas, J. M. Pure Appl. Chem. 1988, 60, 1517. (d) Henglein, A. Chem. Rev. 1989, 89, 1861. (e) A superb series of papers, complete with a record of the insightful comments by the experts attending the conference, is available in: Faraday Discuss. 1991, 92, 1-300. (f) Bradley, J. S. In Clusters and Colloids. From Theory to Applications; Schmidt, G., Ed.; VCH Publishers: New York, 1994; pp 459-544. (g) Schmid, G. In Aspects of Homogeneous Catalysis; Ugo, R., Ed.; Kluwer: Dordrecht, 1990; Vol. 7, Chapter 1. (h) Henglein, A. J. Chem. Phys. 1993, 97, 5457. (i) Belloni, J. Curr. Opin. Colloid Interface Sci. 1996, 1, 184. (j) A list of more than 80 lead references is compiled in: Bönnemann, K.; Braun, G.; Brijoux, W.; Brinkmann, R.; Schulze Tilling, A., Seevogel, K.; Siepen, K. J. Organo. Met. Chem. 1996, 520, 143.
11. 4b
12. (b) Andres, R. P.; Averback, R. S.; Brown, W. L.; Bras, L. E.; Goddard, W. A., III; Kaldor, A.; Louie, S. G.; Moscovits, M.; Peercy, P. S.; Riley, S. J.; Siegel, R. W.; Spaepen, F.; Wang, Y. J. Mater. Res. 1989, 4, 704.
13. (c) Professor Reetz's electrochemical synthesis of transition-metal nanoclusters is noteworthy: Reetz, M.; Helbig, W. J. Am. Chem. Soc. 1994, 116, 7401.
14. y clusters increases (i.e., in comparison to the Cu(O) clusters).
15. (b) See Tables 1 and 2 in: Maitra, A. J. Phys. Chem. 1984, 88, 5122. Naza'rio, L. M. M.; Hatton, T. A.; Crespo, P. S. G. Langmuir, 1996, 12, 6326. A review of the surfactant AOT (sodium bis(2-ethylhexyl)sulfosuccinate) and its reverse micelles: De, T. K.; Maitra, A. Adv. Colloid Interface. Sci. 1995, 59, 95.
16. (b) See Tables 1 and 2 in: Maitra, A. J. Phys. Chem. 1984, 88, 5122. Naza'rio, L. M. M.; Hatton, T. A.; Crespo, P. S. G. Langmuir, 1996, 12, 6326. A review of the surfactant AOT (sodium bis(2-ethylhexyl)sulfosuccinate) and its reverse micelles: De, T. K.; Maitra, A. Adv. Colloid Interface. Sci. 1995, 59, 95.
17. (b) See Tables 1 and 2 in: Maitra, A. J. Phys. Chem. 1984, 88, 5122. Naza'rio, L. M. M.; Hatton, T. A.; Crespo, P. S. G. Langmuir, 1996, 12, 6326. A review of the surfactant AOT (sodium bis(2-ethylhexyl)sulfosuccinate) and its reverse micelles: De, T. K.; Maitra, A. Adv. Colloid Interface. Sci. 1995, 59, 95.
18. (c) The following authors note that "the shape of these aggregates (reverse micelles) depends on several factors and generally changes from spherical to cylindrical to more complex structures according to the nature of the surfactant counterion (for ionic surfactants), the surfactant, and the water concentration." Sangregorio, C.; Galeotti, M.; Bardi, U.; Baglioni, P. Langmuir 1996, 12, 5800 and references therein,
19. (d) Steigerwald and Brus discuss some of the achievements and the limitations - including the lack of mechanistic understanding - in the use of structured reaction media to provide quite useful, but not yet "on demand", size control in semiconductor nanocluster syntheses: Steigerwald, M. L.; Brus, L. E. Acc. Chem. Res. 1990, 22, 183.
20. (e) Lisiecki, I.; Pileni, M. P. J. Am. Chem. Soc. 1993, 115, 3887. Lisiecki, I.; Pileni, M. P. J. Phys. Chem. 1995, 99, 5077. Lisiecki, I.; Billoudet, F.; Pileni, M. P. J. Phys. Chem. 1996, 100, 4160.
21. (e) Lisiecki, I.; Pileni, M. P. J. Am. Chem. Soc. 1993, 115, 3887. Lisiecki, I.; Pileni, M. P. J. Phys. Chem. 1995, 99, 5077. Lisiecki, I.; Billoudet, F.; Pileni, M. P. J. Phys. Chem. 1996, 100, 4160.
22. (e) Lisiecki, I.; Pileni, M. P. J. Am. Chem. Soc. 1993, 115, 3887. Lisiecki, I.; Pileni, M. P. J. Phys. Chem. 1995, 99, 5077. Lisiecki, I.; Billoudet, F.; Pileni, M. P. J. Phys. Chem. 1996, 100, 4160.
23. - (X = Br, Cl)/hexane/hexanol: Wilcoxon, J. P.; Williamson, R. L.; Braughman, R. J. Chem. Phys. 1993, 98, 9933. Wilcoxon, J. P.; Martino, A.; Braughman, R.; Klavetter, E.; Sylwester, A. P. Mater. Res. Soc. Symp. 1994, 357, 311. Venturini, E. L.; Wilcoxon, J. P.; Newcomer, P. P. Mater. Res. Soc. Symp. 1993, 286, 131. Wilcoxon, J. P.; Samara, G. A. Phys. Rev. B 1995, 51, 7299. This work provides detailed insights into experimental variables one must control in these systems to obtain the best, reproducible nanoparticles (e.g., the removal of water, oxygen, and sources of inhomogeneous nucleation such as gas bubbles or dust particles).
24. - (X = Br, Cl)/hexane/hexanol: Wilcoxon, J. P.; Williamson, R. L.; Braughman, R. J. Chem. Phys. 1993, 98, 9933. Wilcoxon, J. P.; Martino, A.; Braughman, R.; Klavetter, E.; Sylwester, A. P. Mater. Res. Soc. Symp. 1994, 357, 311. Venturini, E. L.; Wilcoxon, J. P.; Newcomer, P. P. Mater. Res. Soc. Symp. 1993, 286, 131. Wilcoxon, J. P.; Samara, G. A. Phys. Rev. B 1995, 51, 7299. This work provides detailed insights into experimental variables one must control in these systems to obtain the best, reproducible nanoparticles (e.g., the removal of water, oxygen, and sources of inhomogeneous nucleation such as gas bubbles or dust particles).
25. - (X = Br, Cl)/hexane/hexanol: Wilcoxon, J. P.; Williamson, R. L.; Braughman, R. J. Chem. Phys. 1993, 98, 9933. Wilcoxon, J. P.; Martino, A.; Braughman, R.; Klavetter, E.; Sylwester, A. P. Mater. Res. Soc. Symp. 1994, 357, 311. Venturini, E. L.; Wilcoxon, J. P.; Newcomer, P. P. Mater. Res. Soc. Symp. 1993, 286, 131. Wilcoxon, J. P.; Samara, G. A. Phys. Rev. B 1995, 51, 7299. This work provides detailed insights into experimental variables one must control in these systems to obtain the best, reproducible nanoparticles (e.g., the removal of water, oxygen, and sources of inhomogeneous nucleation such as gas bubbles or dust particles).
26. - (X = Br, Cl)/hexane/hexanol: Wilcoxon, J. P.; Williamson, R. L.; Braughman, R. J. Chem. Phys. 1993, 98, 9933. Wilcoxon, J. P.; Martino, A.; Braughman, R.; Klavetter, E.; Sylwester, A. P. Mater. Res. Soc. Symp. 1994, 357, 311. Venturini, E. L.; Wilcoxon, J. P.; Newcomer, P. P. Mater. Res. Soc. Symp. 1993, 286, 131. Wilcoxon, J. P.; Samara, G. A. Phys. Rev. B 1995, 51, 7299. This work provides detailed insights into experimental variables one must control in these systems to obtain the best, reproducible nanoparticles (e.g., the removal of water, oxygen, and sources of inhomogeneous nucleation such as gas bubbles or dust particles).
27. 2c by Reetz.
28. (a) Part I: Watzky, M. A.; Aiken, J. D. III; Widegren, J.; Finke, R. G., submitted ("A New Kinetic Method to Follow Transition-Metal Nanocluster Formation Based on Catalytic Activity and the Pseudo-elementary Step Concept").
29. (b) Part II: Watzky, M. A.; Finke, R. G. J. Am. Chem. Soc., in press ("Transition Metal Nanocluster Formation Kinetic and Mechanistic Studies. A New Mechanism When Hydrogen Is the Reductant: Slow, Continuous Nucleation and Fast Autocatalytic Surface Growth").
30. ∼2400 Nanoclusters").
31. (d) Part V: Widegren, J.; Watzky, M. A.; Finke, R. G., experiments in progress.
32. ∼900 nanoclusters, plus definitions of terms such as "colloids and nanocolloids vs nanoclusters", "near-monodisperse", and other useful terms, see: Aiken, J. D. III; Lin, Y.; Finke, R. G. J. Mol. Catal. A: Chem. 1996, 114, 29.
33. (a) Lin, Y.; Finke, R. G. Inorg. Chem. 1994, 33, 4891.
34. (b) Lin, Y.; Finke, R. G. J. Am. Chem. Soc. 1994, 116, 8335.
35. 6b a definition that would exclude nanoclusters. (a) Whitesides, G. M. Sci. Am. 1995, Sept, 146. (b) Whitesides, G. M.; Mathias, J. P.; Seto, C. T. Science 1991, 254, 1312 and references therein. (c) A review of organic and bioorganic self-assembly, one that reveals the dearth of kinetic and mechanistic studies: Philip, D.; Stoddart, J. F. Angew. Chem., Int. Eng. Ed. 1996, 35, 1154 and references therein. (d) Dagani, R. in Chem. Eng. News, 1996, July 8, 26.
36. 6b a definition that would exclude nanoclusters. (a) Whitesides, G. M. Sci. Am. 1995, Sept, 146. (b) Whitesides, G. M.; Mathias, J. P.; Seto, C. T. Science 1991, 254, 1312 and references therein. (c) A review of organic and bioorganic self-assembly, one that reveals the dearth of kinetic and mechanistic studies: Philip, D.; Stoddart, J. F. Angew. Chem., Int. Eng. Ed. 1996, 35, 1154 and references therein. (d) Dagani, R. in Chem. Eng. News, 1996, July 8, 26.
37. 6b a definition that would exclude nanoclusters. (a) Whitesides, G. M. Sci. Am. 1995, Sept, 146. (b) Whitesides, G. M.; Mathias, J. P.; Seto, C. T. Science 1991, 254, 1312 and references therein. (c) A review of organic and bioorganic self-assembly, one that reveals the dearth of kinetic and mechanistic studies: Philip, D.; Stoddart, J. F. Angew. Chem., Int. Eng. Ed. 1996, 35, 1154 and references therein. (d) Dagani, R. in Chem. Eng. News, 1996, July 8, 26.
38. 6b a definition that would exclude nanoclusters. (a) Whitesides, G. M. Sci. Am. 1995, Sept, 146. (b) Whitesides, G. M.; Mathias, J. P.; Seto, C. T. Science 1991, 254, 1312 and references therein. (c) A review of organic and bioorganic self-assembly, one that reveals the dearth of kinetic and mechanistic studies: Philip, D.; Stoddart, J. F. Angew. Chem., Int. Eng. Ed. 1996, 35, 1154 and references therein. (d) Dagani, R. in Chem. Eng. News, 1996, July 8, 26.
39. Classic organic anionic living polymerization: (a) Szwarc, M. Nature 1956, 178, 1168. (b) Szwarc, M. In Advances in Polymer Science; Springer-Verlag: Berlin, 1983; Vol. 49.
40. Classic organic anionic living polymerization: (a) Szwarc, M. Nature 1956, 178, 1168. (b) Szwarc, M. In Advances in Polymer Science; Springer-Verlag: Berlin, 1983; Vol. 49.
41. 28 Ir(O)-Ir(O) metal -metal bonds per Ir(0) present in these smaller nanoclusters.
42. (a) Schmid, G.; West, H.; Malm, J.-O.; Bovin, J.-O.; Grenthe, C. Chem. Eur. J., 1996, 2, 147 and references therein. Note that these authors use the "seed growth" method to prepare bimetallic nanoclusters.
43. (b) Michel, J. B.; Schwartz, J. T. In Catalyst Preparation Science; Delmon, B., Grange, P., Jacobs, P. A., Poncelet, G., Eds.; Elsevier: New York, 1987; Vol. IV, pp 669-687.
44. (c) Steigerwald, M. L.; Brus, L. Acc. Chem. Res. 1990, 23, 183. These authors specifically note the concept of "living polymers" (see p 184) in the case of their CdSe or CdS nanoclusters.
45. (d) Klabunde also has noted the analogous "living colloidal palladium" concept: Cardenas-Trivino, G.; Klabunde, K. J.; Dale, E. B. Langmuir 1987, 3, 986. Franklin, M. T.; Klabunde, K. J. In High Energy Processes in Organometallic Chemistry; Suslick, K. S., Ed.; ACS Symposia Series 333; American Chemical Society, Washington, DC, 1987; Chapter 15, p 246.
46. (d) Klabunde also has noted the analogous "living colloidal palladium" concept: Cardenas-Trivino, G.; Klabunde, K. J.; Dale, E. B. Langmuir 1987, 3, 986. Franklin, M. T.; Klabunde, K. J. In High Energy Processes in Organometallic Chemistry; Suslick, K. S., Ed.; ACS Symposia Series 333; American Chemical Society, Washington, DC, 1987; Chapter 15, p 246.
47. (e) Transition-metal magic numbers nanoclusters: see refs 26 and 27 provided as part of the present paper.
48. (f) Klots, T. D.; Winter, B. J.; Parks, E. K.; Riley, S. J. J. Chem. Phys. 1990, 92, 2110.
49. 4 - probably underlies the preparation of a narrower size distributions of Ni heterogeneous catalysts: Che, M.; Cheng, Z. X.; Louis, C. J. Am. Chem. Soc. 1995, 117, 2008.
50. ∼561: Amiens, C.; de Caro, D.; Chaudret, B.; Bradley, J.; Mazel, R.; Roucau, C. J. Am. Chem. Soc. 1993, 115, 11638. See also: Rodriguez, A.; Amiens, C.; Chaudret, B.; Casanove, M.-J.; Lecante, P.; Bradley, J. Chem. Mater. 1996, 8, 1978.
51. ∼561: Amiens, C.; de Caro, D.; Chaudret, B.; Bradley, J.; Mazel, R.; Roucau, C. J. Am. Chem. Soc. 1993, 115, 11638. See also: Rodriguez, A.; Amiens, C.; Chaudret, B.; Casanove, M.-J.; Lecante, P.; Bradley, J. Chem. Mater. 1996, 8, 1978.
52. ∼561: Amiens, C.; de Caro, D.; Chaudret, B.; Bradley, J.; Mazel, R.; Roucau, C. J. Am. Chem. Soc. 1993, 115, 11638. See also: Rodriguez, A.; Amiens, C.; Chaudret, B.; Casanove, M.-J.; Lecante, P.; Bradley, J. Chem. Mater. 1996, 8, 1978.
53. ∼561: Amiens, C.; de Caro, D.; Chaudret, B.; Bradley, J.; Mazel, R.; Roucau, C. J. Am. Chem. Soc. 1993, 115, 11638. See also: Rodriguez, A.; Amiens, C.; Chaudret, B.; Casanove, M.-J.; Lecante, P.; Bradley, J. Chem. Mater. 1996, 8, 1978.
54. ∼561: Amiens, C.; de Caro, D.; Chaudret, B.; Bradley, J.; Mazel, R.; Roucau, C. J. Am. Chem. Soc. 1993, 115, 11638. See also: Rodriguez, A.; Amiens, C.; Chaudret, B.; Casanove, M.-J.; Lecante, P.; Bradley, J. Chem. Mater. 1996, 8, 1978.
55. ∼561: Amiens, C.; de Caro, D.; Chaudret, B.; Bradley, J.; Mazel, R.; Roucau, C. J. Am. Chem. Soc. 1993, 115, 11638. See also: Rodriguez, A.; Amiens, C.; Chaudret, B.; Casanove, M.-J.; Lecante, P.; Bradley, J. Chem. Mater. 1996, 8, 1978.
56. Pohl, M.; Lyon, D. K.; Mizumo, N.; Nomiya, K.; Finke, R. G. Inorg. Chem. 1995, 34, 1413.
57. Weiner, H. W.; Aiken, J. D. III; Finke, R. G. Inorg. Chem. 1996, 35, 7905.
58. Press: W. H.; Flannery, B. P.; Teukolsky, S. A.; Vetterling, W. T. Numerical Recipes; Cambridge University: Cambridge, 1989.
59. solution).
60. (b) Lyon, D. K. Ph.D. Dissertation, University of Oregon, 1990.
61. psj.
62. 4b
63. 4b,16b).
64. 5b The effect of cyclohexene is not fully understood and, hence, is still under investigation.
65. 0/2).
66. 0 = 1.2 mM, and no cyclohexene.
67. 5b) about these important issues. This is one reason we carefully cite herein our TEM sampling methods, our multiple TEM control experiments (see Experimental Section) and also why we cite the number of particles counted with each TEM and its associated histogram.
68. n sample is inversely dependent on the cluster size, n.
69. 4b
70. 4b
71. 2(fit)/2.5).
72. 4b Hence, those results independently predict the small dependence of size upon temperature confirmed as part of the present study.
73. Lead references to the concept of "magic number" clusters: (a) Teo, B. K.; Sloane, N. J. A. Inorg. Chem. 1985, 24, 4545. (b) Wells, A. F. Structural Inorganic Chemistry, 4th ed.; Clarendon Press: Oxford, 1975. Pages 123 and 131 provide a concise discussion of sphere packings and their relationships to the 12 nearest-neighbor atoms that define cubooctahedral (ccp, or equivalently, fcc) and twinned cubooctahedral (hcp) discrete structures. (c) Howie, A. Faraday Discuss. 1991, 92, 1 (see pp 2-3). (d) Klots, T. D.; Winter, B. J.; Parks, E. K; Riley, S. J. J. Chem. Phys. 1990, 92, 2110.
74. Lead references to the concept of "magic number" clusters: (a) Teo, B. K.; Sloane, N. J. A. Inorg. Chem. 1985, 24, 4545. (b) Wells, A. F. Structural Inorganic Chemistry, 4th ed.; Clarendon Press: Oxford, 1975. Pages 123 and 131 provide a concise discussion of sphere packings and their relationships to the 12 nearest-neighbor atoms that define cubooctahedral (ccp, or equivalently, fcc) and twinned cubooctahedral (hcp) discrete structures. (c) Howie, A. Faraday Discuss. 1991, 92, 1 (see pp 2-3). (d) Klots, T. D.; Winter, B. J.; Parks, E. K; Riley, S. J. J. Chem. Phys. 1990, 92, 2110.
75. Lead references to the concept of "magic number" clusters: (a) Teo, B. K.; Sloane, N. J. A. Inorg. Chem. 1985, 24, 4545. (b) Wells, A. F. Structural Inorganic Chemistry, 4th ed.; Clarendon Press: Oxford, 1975. Pages 123 and 131 provide a concise discussion of sphere packings and their relationships to the 12 nearest-neighbor atoms that define cubooctahedral (ccp, or equivalently, fcc) and twinned cubooctahedral (hcp) discrete structures. (c) Howie, A. Faraday Discuss. 1991, 92, 1 (see pp 2-3). (d) Klots, T. D.; Winter, B. J.; Parks, E. K; Riley, S. J. J. Chem. Phys. 1990, 92, 2110.
76. Lead references to the concept of "magic number" clusters: (a) Teo, B. K.; Sloane, N. J. A. Inorg. Chem. 1985, 24, 4545. (b) Wells, A. F. Structural Inorganic Chemistry, 4th ed.; Clarendon Press: Oxford, 1975. Pages 123 and 131 provide a concise discussion of sphere packings and their relationships to the 12 nearest-neighbor atoms that define cubooctahedral (ccp, or equivalently, fcc) and twinned cubooctahedral (hcp) discrete structures. (c) Howie, A. Faraday Discuss. 1991, 92, 1 (see pp 2-3). (d) Klots, T. D.; Winter, B. J.; Parks, E. K; Riley, S. J. J. Chem. Phys. 1990, 92, 2110.
77. 2bc
78. 27c does not provide a mechanistic explanation for magic number nanoclusters of either of the two known classes.
79. (c) Fojtik, A.; Weller, H.; Koch, U.; Henglein, A. Ber. Bungen-Ges. Phys. Chem. 1984, 88, 969.
80. (d) Noteworty is Bawendi and co-workers' brief discussion, on p 8708, of magic number sizes in CdE (E = S, Se, Te) semiconductor particles in terms of a thermodynamic "bottleneck" that reduces the driving force for further growth. Murray, C. B.; Norris, D. J.; Bawendi, M. G. J. Am. Chem. Soc. 1993, 115, 8706. Note, however, that this brief statement is ambiguous in whether or not the production of CdE is ultimately thermodynamically or kinetically controlled.
81. 38b,c reveals the driving force for Ir(0), nanoparticles to aggregate to the thermodynamically favored, low-surface-area solid, thereby revealing that this and similar nanocluster syntheses are under kinetic control.
82. 29a-d work which provides some precedent for the Ir cluster growth step presented herein. However, compelling evidence for the autocatalytic nature of this key step has not been previously described, (a) McCarthy, T. J.; Shih, Y.-S.; Whitesides, G. M. Proc. Natl. Acad. Sci. U.S.A. 1981, 78, 4649. (b) Whitesides, G. M.; Hackett, M.; Brainard, R. L.; LaVelleye, J. P.-P.; Sowinski, A. F.; Izumi, A. N.; Moore, S. S.; Brown, D. W.; Staudt, E. M. Organometallics 1985, 4, 1819. (c) Miller, T. M.; Izumi, A. N.; Shih, Y.-S.; Whitesides, G. M. J. Am. Chem. Soc. 1988, 110, 3146. (d) Lee, T. R.; Whitesides, G. M. Acc. Chem. Res. 1992, 25, 266 and references therein to the other papers in this series.
83. 29a-d work which provides some precedent for the Ir cluster growth step presented herein. However, compelling evidence for the autocatalytic nature of this key step has not been previously described, (a) McCarthy, T. J.; Shih, Y.-S.; Whitesides, G. M. Proc. Natl. Acad. Sci. U.S.A. 1981, 78, 4649. (b) Whitesides, G. M.; Hackett, M.; Brainard, R. L.; LaVelleye, J. P.-P.; Sowinski, A. F.; Izumi, A. N.; Moore, S. S.; Brown, D. W.; Staudt, E. M. Organometallics 1985, 4, 1819. (c) Miller, T. M.; Izumi, A. N.; Shih, Y.-S.; Whitesides, G. M. J. Am. Chem. Soc. 1988, 110, 3146. (d) Lee, T. R.; Whitesides, G. M. Acc. Chem. Res. 1992, 25, 266 and references therein to the other papers in this series.
84. 29a-d work which provides some precedent for the Ir cluster growth step presented herein. However, compelling evidence for the autocatalytic nature of this key step has not been previously described, (a) McCarthy, T. J.; Shih, Y.-S.; Whitesides, G. M. Proc. Natl. Acad. Sci. U.S.A. 1981, 78, 4649. (b) Whitesides, G. M.; Hackett, M.; Brainard, R. L.; LaVelleye, J. P.-P.; Sowinski, A. F.; Izumi, A. N.; Moore, S. S.; Brown, D. W.; Staudt, E. M. Organometallics 1985, 4, 1819. (c) Miller, T. M.; Izumi, A. N.; Shih, Y.-S.; Whitesides, G. M. J. Am. Chem. Soc. 1988, 110, 3146. (d) Lee, T. R.; Whitesides, G. M. Acc. Chem. Res. 1992, 25, 266 and references therein to the other papers in this series.
85. 29a-d work which provides some precedent for the Ir cluster growth step presented herein. However, compelling evidence for the autocatalytic nature of this key step has not been previously described, (a) McCarthy, T. J.; Shih, Y.-S.; Whitesides, G. M. Proc. Natl. Acad. Sci. U.S.A. 1981, 78, 4649. (b) Whitesides, G. M.; Hackett, M.; Brainard, R. L.; LaVelleye, J. P.-P.; Sowinski, A. F.; Izumi, A. N.; Moore, S. S.; Brown, D. W.; Staudt, E.
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93. 2 as a preferred reducing agent.
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112. 38 We note, however, that none of these issues - ones expected given the early state of bimetallic nanocluster chemistry - detracts whatsoever form the significance of Professor Schmid's important early contribution or from the exciting prospects their work foretells.
113. (b) Boudart, M.; Dje'ga-Mariadassou, G. Kinetics of Heterogeneous Catalytic Reactions; Princeton University Press: Princeton, NJ, 1984.
114. (c) Naito, S.; Tanimoto, M. J. Chem. Soc. Chem. Commun. 1988, 832 and refs 1-3 therein.
115. 36a
116. (b) See the TEM in Figure 2 elsewhere showing "Ag staining" of Pt nanoclusters (i.e., Ag growth on Pt nucleation sites; Figure 2). Ketelson, H. M.; Brook, M. A.; Pelto, R.; Heng, Y. M. Chem. Mater. 1996, 8, 2195; see also refs 26 and 27 therein to Cu, Ni and other metal deposition on, for example, preformed Pd and Pt colloids.
117. (c) Vidali, G. in Nanoparticles in Solids and Solutions; Fendler, J. H., Dékány, I., Eds.; Kluwer: The Netherlands, 1996; pp 17-33.
118. Lead references to studies of bimetallic nanoclusters in catalysis: (a) Au/Pt and Pd/Pt nanoclusters: Schmidt, G.; West, H.; Mehles, H.; Lenhert, A. Inorg. Chem. 1997, 36, 891 and refs 26 and 27 therein to layer migration phenomena, (b) Au/Pd and Pd/Au: Schmidt, G.; West, H.; Malm, J.-O.; Bovin, J.-O.; Grenthe, C. Eur. Chem. J. 1996, 2, 147. (c) Reetz, M. T.; Breinbrauer, R.; Wanninger, K. Tet. Lett. 1996, 37, 4499. (d) Pd/Ni: Toshima, N.; Lu, P. Chem. Lett. 1996, 729. (e) Pt/Co: Yu, W.; Wang, Y.; Liu, H.; Zheng, W. J. Mol. Catal. A: Chem. 1996, 112, 105.
119. Lead references to studies of bimetallic nanoclusters in catalysis: (a) Au/Pt and Pd/Pt nanoclusters: Schmidt, G.; West, H.; Mehles, H.; Lenhert, A. Inorg. Chem. 1997, 36, 891 and refs 26 and 27 therein to layer migration phenomena, (b) Au/Pd and Pd/Au: Schmidt, G.; West, H.; Malm, J.-O.; Bovin, J.-O.; Grenthe, C. Eur. Chem. J. 1996, 2, 147. (c) Reetz, M. T.; Breinbrauer, R.; Wanninger, K. Tet. Lett. 1996, 37, 4499. (d) Pd/Ni: Toshima, N.; Lu, P. Chem. Lett. 1996, 729. (e) Pt/Co: Yu, W.; Wang, Y.; Liu, H.; Zheng, W. J. Mol. Catal. A: Chem. 1996, 112, 105.
120. Lead references to studies of bimetallic nanoclusters in catalysis: (a) Au/Pt and Pd/Pt nanoclusters: Schmidt, G.; West, H.; Mehles, H.; Lenhert, A. Inorg. Chem. 1997, 36, 891 and refs 26 and 27 therein to layer migration phenomena, (b) Au/Pd and Pd/Au: Schmidt, G.; West, H.; Malm, J.-O.; Bovin, J.-O.; Grenthe, C. Eur. Chem. J. 1996, 2, 147. (c) Reetz, M. T.; Breinbrauer, R.; Wanninger, K. Tet. Lett. 1996, 37, 4499. (d) Pd/Ni: Toshima, N.; Lu, P. Chem. Lett. 1996, 729. (e) Pt/Co: Yu, W.; Wang, Y.; Liu, H.; Zheng, W. J. Mol. Catal. A: Chem. 1996, 112, 105.
121. Lead references to studies of bimetallic nanoclusters in catalysis: (a) Au/Pt and Pd/Pt nanoclusters: Schmidt, G.; West, H.; Mehles, H.; Lenhert, A. Inorg. Chem. 1997, 36, 891 and refs 26 and 27 therein to layer migration phenomena, (b) Au/Pd and Pd/Au: Schmidt, G.; West, H.; Malm, J.-O.; Bovin, J.-O.; Grenthe, C. Eur. Chem. J. 1996, 2, 147. (c) Reetz, M. T.; Breinbrauer, R.; Wanninger, K. Tet. Lett. 1996, 37, 4499. (d) Pd/Ni: Toshima, N.; Lu, P. Chem. Lett. 1996, 729. (e) Pt/Co: Yu, W.; Wang, Y.; Liu, H.; Zheng, W. J. Mol. Catal. A: Chem. 1996, 112, 105.
122. Lead references to studies of bimetallic nanoclusters in catalysis: (a) Au/Pt and Pd/Pt nanoclusters: Schmidt, G.; West, H.; Mehles, H.; Lenhert, A. Inorg. Chem. 1997, 36, 891 and refs 26 and 27 therein to layer migration phenomena, (b) Au/Pd and Pd/Au: Schmidt, G.; West, H.; Malm, J.-O.; Bovin, J.-O.; Grenthe, C. Eur. Chem. J. 1996, 2, 147. (c) Reetz, M. T.; Breinbrauer, R.; Wanninger, K. Tet. Lett. 1996, 37, 4499. (d) Pd/Ni: Toshima, N.; Lu, P. Chem. Lett. 1996, 729. (e) Pt/Co: Yu, W.; Wang, Y.; Liu, H.; Zheng, W. J. Mol. Catal. A: Chem. 1996, 112, 105.
123. Other lead references to the synthesis and characterization of bimetallic nanoclusters: (a) Pf/Pd oxide: Harada, M.; Asakura, K.; Ueki, Y.; Toshima, N. J. Chem. Phys. 1992, 96, 9730. Toshima, N.; Harada, M.; Yonezawa, T.; Kushihashi, K. Asakura, K. J. Chem. Phys. 1991, 95, 7448. Toshima, N.; Harada, M.; Yonezawa, T.; Hirai, H. Chem. Lett. 1989, 1769. (b) Pt/Pd oxide: Kolbe, U.; Quaiser, S. A.; Winter, M.; Reetz, M. T. Chem. Mater. 1996, 8, 1889. (c) Pd/Ni, Fe/Co, Co/Ni: Reetz, M. T.; Helbig, W.; Quaiser, S. A. Chem. Mater. 1995, 7, 2227. (d) Au/Pt, Au/Pd: Schmid, G.; Lenhert, A.; Mulm, J.-O.; Bovin, J.-O. Angew. Chem., Int. Engl. Ed. 1991, 30, 874. (e) Pd/Cu: Bradley, J. S.; Hill, E. W.; Klein, C.; Chaduret, B.; Dutell, A. Chem. Mater. 1993, 5, 254. (f) Pd/Au: Sermon, P. A.; Thomas, J. M.; Keryou, K.; Millward, G. R. Angew. Chem., Int. Eng. Ed. 1987, 26, 918. (g) Pt/Ru: Richard, D.; Couves, J. W.; Thomas, J. M. Faraday Discuss. 1991, 92, 109.
124. Other lead references to the synthesis and characterization of bimetallic nanoclusters: (a) Pf/Pd oxide: Harada, M.; Asakura, K.; Ueki, Y.; Toshima, N. J. Chem. Phys. 1992, 96, 9730. Toshima, N.; Harada, M.; Yonezawa, T.; Kushihashi, K. Asakura, K. J. Chem. Phys. 1991, 95, 7448. Toshima, N.; Harada, M.; Yonezawa, T.; Hirai, H. Chem. Lett. 1989, 1769. (b) Pt/Pd oxide: Kolbe, U.; Quaiser, S. A.; Winter, M.; Reetz, M. T. Chem. Mater. 1996, 8, 1889. (c) Pd/Ni, Fe/Co, Co/Ni: Reetz, M. T.; Helbig, W.; Quaiser, S. A. Chem. Mater. 1995, 7, 2227. (d) Au/Pt, Au/Pd: Schmid, G.; Lenhert, A.; Mulm, J.-O.; Bovin, J.-O. Angew. Chem., Int. Engl. Ed. 1991, 30, 874. (e) Pd/Cu: Bradley, J. S.; Hill, E. W.; Klein, C.; Chaduret, B.; Dutell, A. Chem. Mater. 1993, 5, 254. (f) Pd/Au: Sermon, P. A.; Thomas, J. M.; Keryou, K.; Millward, G. R. Angew. Chem., Int. Eng. Ed. 1987, 26, 918. (g) Pt/Ru: Richard, D.; Couves, J. W.; Thomas, J. M. Faraday Discuss. 1991, 92, 109.
125. Other lead references to the synthesis and characterization of bimetallic nanoclusters: (a) Pf/Pd oxide: Harada, M.; Asakura, K.; Ueki, Y.; Toshima, N. J. Chem. Phys. 1992, 96, 9730. Toshima, N.; Harada, M.; Yonezawa, T.; Kushihashi, K. Asakura, K. J. Chem. Phys. 1991, 95, 7448. Toshima, N.; Harada, M.; Yonezawa, T.; Hirai, H. Chem. Lett. 1989, 1769. (b) Pt/Pd oxide: Kolbe, U.; Quaiser, S. A.; Winter, M.; Reetz, M. T. Chem. Mater. 1996, 8, 1889. (c) Pd/Ni, Fe/Co, Co/Ni: Reetz, M. T.; Helbig, W.; Quaiser, S. A. Chem. Mater. 1995, 7, 2227. (d) Au/Pt, Au/Pd: Schmid, G.; Lenhert, A.; Mulm, J.-O.; Bovin, J.-O. Angew. Chem., Int. Engl. Ed. 1991, 30, 874. (e) Pd/Cu: Bradley, J. S.; Hill, E. W.; Klein, C.; Chaduret, B.; Dutell, A. Chem. Mater. 1993, 5, 254. (f) Pd/Au: Sermon, P. A.; Thomas, J. M.; Keryou, K.; Millward, G. R. Angew. Chem., Int. Eng. Ed. 1987, 26, 918. (g) Pt/Ru: Richard, D.; Couves, J. W.; Thomas, J. M. Faraday Discuss. 1991, 92, 109.
126. Other lead references to the synthesis and characterization of bimetallic nanoclusters: (a) Pf/Pd oxide: Harada, M.; Asakura, K.; Ueki, Y.; Toshima, N. J. Chem. Phys. 1992, 96, 9730. Toshima, N.; Harada, M.; Yonezawa, T.; Kushihashi, K. Asakura, K. J. Chem. Phys. 1991, 95, 7448. Toshima, N.; Harada, M.; Yonezawa, T.; Hirai, H. Chem. Lett. 1989, 1769. (b) Pt/Pd oxide: Kolbe, U.; Quaiser, S. A.; Winter, M.; Reetz, M. T. Chem. Mater. 1996, 8, 1889. (c) Pd/Ni, Fe/Co, Co/Ni: Reetz, M. T.; Helbig, W.; Quaiser, S. A. Chem. Mater. 1995, 7, 2227. (d) Au/Pt, Au/Pd: Schmid, G.; Lenhert, A.; Mulm, J.-O.; Bovin, J.-O. Angew. Chem., Int. Engl. Ed. 1991, 30, 874. (e) Pd/Cu: Bradley, J. S.; Hill, E. W.; Klein, C.; Chaduret, B.; Dutell, A. Chem. Mater. 1993, 5, 254. (f) Pd/Au: Sermon, P. A.; Thomas, J. M.; Keryou, K.; Millward, G. R. Angew. Chem., Int. Eng. Ed. 1987, 26, 918. (g) Pt/Ru: Richard, D.; Couves, J. W.; Thomas, J. M. Faraday Discuss. 1991, 92, 109.
127. Other lead references to the synthesis and characterization of bimetallic nanoclusters: (a) Pf/Pd oxide: Harada, M.; Asakura, K.; Ueki, Y.; Toshima, N. J. Chem. Phys. 1992, 96, 9730. Toshima, N.; Harada, M.; Yonezawa, T.; Kushihashi, K. Asakura, K. J. Chem. Phys. 1991, 95, 7448. Toshima, N.; Harada, M.; Yonezawa, T.; Hirai, H. Chem. Lett. 1989, 1769. (b) Pt/Pd oxide: Kolbe, U.; Quaiser, S. A.; Winter, M.; Reetz, M. T. Chem. Mater. 1996, 8, 1889. (c) Pd/Ni, Fe/Co, Co/Ni: Reetz, M. T.; Helbig, W.; Quaiser, S. A. Chem. Mater. 1995, 7, 2227. (d) Au/Pt, Au/Pd: Schmid, G.; Lenhert, A.; Mulm, J.-O.; Bovin, J.-O. Angew. Chem., Int. Engl. Ed. 1991, 30, 874. (e) Pd/Cu: Bradley, J. S.; Hill, E. W.; Klein, C.; Chaduret, B.; Dutell, A. Chem. Mater. 1993, 5, 254. (f) Pd/Au: Sermon, P. A.; Thomas, J. M.; Keryou, K.; Millward, G. R. Angew. Chem., Int. Eng. Ed. 1987, 26, 918. (g) Pt/Ru: Richard, D.; Couves, J. W.; Thomas, J. M. Faraday Discuss. 1991, 92, 109.
128. Other lead references to the synthesis and characterization of bimetallic nanoclusters: (a) Pf/Pd oxide: Harada, M.; Asakura, K.; Ueki, Y.; Toshima, N. J. Chem. Phys. 1992, 96, 9730. Toshima, N.; Harada, M.; Yonezawa, T.; Kushihashi, K. Asakura, K. J. Chem. Phys. 1991, 95, 7448. Toshima, N.; Harada, M.; Yonezawa, T.; Hirai, H. Chem. Lett. 1989, 1769. (b) Pt/Pd oxide: Kolbe, U.; Quaiser, S. A.; Winter, M.; Reetz, M. T. Chem. Mater. 1996, 8, 1889. (c) Pd/Ni, Fe/Co, Co/Ni: Reetz, M. T.; Helbig, W.; Quaiser, S. A. Chem. Mater. 1995, 7, 2227. (d) Au/Pt, Au/Pd: Schmid, G.; Lenhert, A.; Mulm, J.-O.; Bovin, J.-O. Angew. Chem., Int. Engl. Ed. 1991, 30, 874. (e) Pd/Cu: Bradley, J. S.; Hill, E. W.; Klein, C.; Chaduret, B.; Dutell, A. Chem. Mater. 1993, 5, 254. (f) Pd/Au: Sermon, P. A.; Thomas, J. M.; Keryou, K.; Millward, G. R. Angew. Chem., Int. Eng. Ed. 1987, 26, 918. (g) Pt/Ru: Richard, D.; Couves, J. W.; Thomas, J. M. Faraday Discuss. 1991, 92, 109.
129. Other lead references to the synthesis and characterization of bimetallic nanoclusters: (a) Pf/Pd oxide: Harada, M.; Asakura, K.; Ueki, Y.; Toshima, N. J. Chem. Phys. 1992, 96, 9730. Toshima, N.; Harada, M.; Yonezawa, T.; Kushihashi, K. Asakura, K. J. Chem. Phys. 1991, 95, 7448. Toshima, N.; Harada, M.; Yonezawa, T.; Hirai, H. Chem. Lett. 1989, 1769. (b) Pt/Pd oxide: Kolbe, U.; Quaiser, S. A.; Winter, M.; Reetz, M. T. Chem. Mater. 1996, 8, 1889. (c) Pd/Ni, Fe/Co, Co/Ni: Reetz, M. T.; Helbig, W.; Quaiser, S. A. Chem. Mater. 1995, 7, 2227. (d) Au/Pt, Au/Pd: Schmid, G.; Lenhert, A.; Mulm, J.-O.; Bovin, J.-O. Angew. Chem., Int. Engl. Ed. 1991, 30, 874. (e) Pd/Cu: Bradley, J. S.; Hill, E. W.; Klein, C.; Chaduret, B.; Dutell, A. Chem. Mater. 1993, 5, 254. (f) Pd/Au: Sermon, P. A.; Thomas, J. M.; Keryou, K.; Millward, G. R. Angew. Chem., Int. Eng. Ed. 1987, 26, 918. (g) Pt/Ru: Richard, D.; Couves, J. W.; Thomas, J. M. Faraday Discuss. 1991, 92, 109.
130. Other lead references to the synthesis and characterization of bimetallic nanoclusters: (a) Pf/Pd oxide: Harada, M.; Asakura, K.; Ueki, Y.; Toshima, N. J. Chem. Phys. 1992, 96, 9730. Toshima, N.; Harada, M.; Yonezawa, T.; Kushihashi, K. Asakura, K. J. Chem. Phys. 1991, 95, 7448. Toshima, N.; Harada, M.; Yonezawa, T.; Hirai, H. Chem. Lett. 1989, 1769. (b) Pt/Pd oxide: Kolbe, U.; Quaiser, S. A.; Winter, M.; Reetz, M. T. Chem. Mater. 1996, 8, 1889. (c) Pd/Ni, Fe/Co, Co/Ni: Reetz, M. T.; Helbig, W.; Quaiser, S. A. Chem. Mater. 1995, 7, 2227. (d) Au/Pt, Au/Pd: Schmid, G.; Lenhert, A.; Mulm, J.-O.; Bovin, J.-O. Angew. Chem., Int. Engl. Ed. 1991, 30, 874. (e) Pd/Cu: Bradley, J. S.; Hill, E. W.; Klein, C.; Chaduret, B.; Dutell, A. Chem. Mater. 1993, 5, 254. (f) Pd/Au: Sermon, P. A.; Thomas, J. M.; Keryou, K.; Millward, G. R. Angew. Chem., Int. Eng. Ed. 1987, 26, 918. (g) Pt/Ru: Richard, D.; Couves, J. W.; Thomas, J. M. Faraday Discuss. 1991, 92, 109.
131. Other lead references to the synthesis and characterization of bimetallic nanoclusters: (a) Pf/Pd oxide: Harada, M.; Asakura, K.; Ueki, Y.; Toshima, N. J. Chem. Phys. 1992, 96, 9730. Toshima, N.; Harada, M.; Yonezawa, T.; Kushihashi, K. Asakura, K. J. Chem. Phys. 1991, 95, 7448. Toshima, N.; Harada, M.; Yonezawa, T.; Hirai, H. Chem. Lett. 1989, 1769. (b) Pt/Pd oxide: Kolbe, U.; Quaiser, S. A.; Winter, M.; Reetz, M. T. Chem. Mater. 1996, 8, 1889. (c) Pd/Ni, Fe/Co, Co/Ni: Reetz, M. T.; Helbig, W.; Quaiser, S. A. Chem. Mater. 1995, 7, 2227. (d) Au/Pt, Au/Pd: Schmid, G.; Lenhert, A.; Mulm, J.-O.; Bovin, J.-O. Angew. Chem., Int. Engl. Ed. 1991, 30, 874. (e) Pd/Cu: Bradley, J. S.; Hill, E. W.; Klein, C.; Chaduret, B.; Dutell, A. Chem. Mater. 1993, 5, 254. (f) Pd/Au: Sermon, P. A.; Thomas, J. M.; Keryou, K.; Millward, G. R. Angew. Chem., Int. Eng. Ed. 1987, 26, 918. (g) Pt/Ru: Richard, D.; Couves, J. W.; Thomas, J. M. Faraday Discuss. 1991, 92, 109.
132. 36a,b
133. (b) Conner, J. A. Top. Curr. Chem. 1997, 71, 71. See pp 76-78.
134. (c) Pichler, G.; Skinner, H. A. In The Chemistry of the Metal-Carbon Bond; Hartley, F. R., Patai, S., Eds.; John Wiley: New York, 1982; see pp 76-80 and Table 13.
135. 3Au alloy nanocluster: Sangregorio, C.; Galeotti, M.; Bardi, U.; Baglioni, P. Langmuir 1996, 12 , 5800. Of interest to the present work is the statement therein that "we have no evidence on the mechanism that leads to mixing at the atomic level".
136. 2, and where true alloys do not form, very likely contain the onionskin structures of Scheme 2.
137. Widegren, J.; Watzky, M. A.; Finke, R. G., experiments in progress.
138. 2 values vs their third row counterparts. Note also that the reductant in these cases is typically an alcohol such as wet MeOH or 2-propanol, suggesting that alcohols are another class of reductants that are operating by the autocatalytic surface-growth mechanism.
139. (b) Hirai, H.; Nakao, Y.; Toshima, N. J. Macromol. Sci.-Chem. 1979, A13, 727.