Transition-metal nanocluster catalysts: Scaled-up synthesis, characterization, storage conditions, stability, and catalytic activity before and after storage of polyoxoanion- and tetrabutylammonium-stabilized Ir(0) nanoclusters

Chemistry of Materials

Volumn 15, Issue 4, 2003, Pages 899-909

  Hornstein, Brooks J ^a   Finke, Richard G ^a  

^a Department of Ecosystem Science and Sustainability   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; ANION; CYCLOHEXENE DERIVATIVE; DEUTERIUM; IRIDIUM; NITROGEN; OXYGEN; SOLVENT; TETRABUTYLAMMONIUM; TRANSITION ELEMENT;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL ANALYSIS; GAS CHROMATOGRAPHY; HYDROGENATION; INFRARED SPECTROSCOPY; PHOSPHORUS NUCLEAR MAGNETIC RESONANCE; PROTON NUCLEAR MAGNETIC RESONANCE; SOLID STATE; STORAGE; SYNTHESIS; TITRIMETRY; TRANSMISSION ELECTRON MICROSCOPY;

EID: 0037465418     PISSN: 08974756     EISSN: None     Source Type: Journal    
DOI: 10.1021/cm020856y     Document Type: Article

References (115)

1. (a) Aiken, J. D., III; Lin, Y.; Finke, R. G. J. Mol. Catal. A: Chem. 1996, 114, 29-51.
2. (b) Aiken, J. D., III; Finke, R. G. J. Mol. Catal. A: Chem. 1999, 145, 1-44.
3. (c) Finke, R. G. Transition-Metal Nanoclusters: Solution-Phase Synthesis, then Characterization and Mechanism of Formation, of Polyoxoanion- and Tetrabutylammonium-Stabilized Nanoclusters. In Metal Nanoparticles: Synthesis, Characterization and Applications; Feldheim, D. L., Foss, C. A., Jr., Eds.; Marcel Dekker: New York, 2002; Chapter 2, pp 17-54
4. 2O, but not organic solvent, soluble.
5. (a) Clusters and Colloids; From Theory to Applications; Schmid, G., Ed.; VCH: New York, 1994.
6. (b) Physics and Chemistry of Metal Cluster Compounds; de Jongh, L. J., Ed.; Kluwer Academic Publishers: Dordrecht, 1994; Vol. 18.
7. (c) Active Metals: Preparation, Characterization, Applications; Furstner, A., Ed.; VCH: Weinheim, 1996.
8. (d) Nanoparticles in Solids and Solutions; Fendler, J. H., Dékány, I., Eds, Kluwer Academic Publishers: Dordrecht, 1996.
9. Lin, Y.; Finke, R. G. J. Am. Chem. Soc. 1994, 116, 8335-8353.
10. Watzky, M. A.; Finke, R. G. J. Am. Chem. Soc. 1997, 119, 10382-10400.
11. Lin, Y.; Finke, R. G. Inorg. Chem. 1994, 33, 4891-4910.
12. Dagani, R. Putting the 'Nano' Into Composites. Chem. Eng. News 1999, June 7, 37.
13. (a) Vargaftik, M. N.; Zagorodnikov, V. P.; Stolyarov, I. P.; Moiseev, I. I.; Likholobov, V. A.; Kochubey, D. I.; Chuvilin, A. L.; Zaikovsky, V. I.; Zamaraev, K. I.; Timofeeva, G. I. J Chem. Soc., Chem. Commun. 1985, 937-939.
14. (b) Vargaftik, M. N.; Zagorodnikov, V. P.; Stolyarov, I. P.; Moiseev, I. I.; Kochubey.; D. I.; Likholobov, V. A.; Chuvilin, A. L.; Zamaraev, K. I. J. Mol. Catal. 1989, 53, 315-348.
15. Schmid, G.; Haarms, M.; Malm, J.-O.; Bovin, J.-O.; Ruitenbeck, J. van; Zandbergen, H. W.; Fu, W. T. J. Am. Chem. Soc. 1993, 115, 2046-2048.
16. Bönnemann, H.; Waldofner, N.; Haubold, H.-G.; Vad, T. Chem. Mater. 2002, 14, 1115-1120.
17. Bönnemann, H.; Brijoux, W.; Brinkmann, R.; Fretzen, R.; Joussen, T.; Koppler, R.; Korall, B.; Neiteler, P.; Richter, J. J. Mol. Catal. 1994, 86, 129.
18. Additional references to Bönnemann and co-workers' studies: (a) Bönnemann, H.; Brijoux, W. NanoStruct. Mater. 1995, 5, 135. (b) Bönnemann, H.; Brinkmann, R.; Neiteler, P. Appl. Organomet. Chem. 1994, 8, 361. (c) Bönnemann, H.; Brinkmann, R.; Koppler, R.; Neiteler, P.; Richter, J. Adv. Mater. 1992, 4, 804. (d) Bönnemann, H.; Brijoux, W.; Brinkman, R.; Dinjus, E.; Fretzen, R.; Joussen, T.; Korall, B. J. Mol. Catal. 1992, 74, 323. (e) Bönnemann, H.; Brijoux, W.; Brinkman, R.; Dinjus, E.; Joussen, T.; Korall, B. Angew. Chem., Int. Ed. Engl. 1991, 30, 1312-1314.
19. Additional references to Bönnemann and co-workers' studies: (a) Bönnemann, H.; Brijoux, W. NanoStruct. Mater. 1995, 5, 135. (b) Bönnemann, H.; Brinkmann, R.; Neiteler, P. Appl. Organomet. Chem. 1994, 8, 361. (c) Bönnemann, H.; Brinkmann, R.; Koppler, R.; Neiteler, P.; Richter, J. Adv. Mater. 1992, 4, 804. (d) Bönnemann, H.; Brijoux, W.; Brinkman, R.; Dinjus, E.; Fretzen, R.; Joussen, T.; Korall, B. J. Mol. Catal. 1992, 74, 323. (e) Bönnemann, H.; Brijoux, W.; Brinkman, R.; Dinjus, E.; Joussen, T.; Korall, B. Angew. Chem., Int. Ed. Engl. 1991, 30, 1312-1314.
20. Additional references to Bönnemann and co-workers' studies: (a) Bönnemann, H.; Brijoux, W. NanoStruct. Mater. 1995, 5, 135. (b) Bönnemann, H.; Brinkmann, R.; Neiteler, P. Appl. Organomet. Chem. 1994, 8, 361. (c) Bönnemann, H.; Brinkmann, R.; Koppler, R.; Neiteler, P.; Richter, J. Adv. Mater. 1992, 4, 804. (d) Bönnemann, H.; Brijoux, W.; Brinkman, R.; Dinjus, E.; Fretzen, R.; Joussen, T.; Korall, B. J. Mol. Catal. 1992, 74, 323. (e) Bönnemann, H.; Brijoux, W.; Brinkman, R.; Dinjus, E.; Joussen, T.; Korall, B. Angew. Chem., Int. Ed. Engl. 1991, 30, 1312-1314.
21. Additional references to Bönnemann and co-workers' studies: (a) Bönnemann, H.; Brijoux, W. NanoStruct. Mater. 1995, 5, 135. (b) Bönnemann, H.; Brinkmann, R.; Neiteler, P. Appl. Organomet. Chem. 1994, 8, 361. (c) Bönnemann, H.; Brinkmann, R.; Koppler, R.; Neiteler, P.; Richter, J. Adv. Mater. 1992, 4, 804. (d) Bönnemann, H.; Brijoux, W.; Brinkman, R.; Dinjus, E.; Fretzen, R.; Joussen, T.; Korall, B. J. Mol. Catal. 1992, 74, 323. (e) Bönnemann, H.; Brijoux, W.; Brinkman, R.; Dinjus, E.; Joussen, T.; Korall, B. Angew. Chem., Int. Ed. Engl. 1991, 30, 1312-1314.
22. Additional references to Bönnemann and co-workers' studies: (a) Bönnemann, H.; Brijoux, W. NanoStruct. Mater. 1995, 5, 135. (b) Bönnemann, H.; Brinkmann, R.; Neiteler, P. Appl. Organomet. Chem. 1994, 8, 361. (c) Bönnemann, H.; Brinkmann, R.; Koppler, R.; Neiteler, P.; Richter, J. Adv. Mater. 1992, 4, 804. (d) Bönnemann, H.; Brijoux, W.; Brinkman, R.; Dinjus, E.; Fretzen, R.; Joussen, T.; Korall, B. J. Mol. Catal. 1992, 74, 323. (e) Bönnemann, H.; Brijoux, W.; Brinkman, R.; Dinjus, E.; Joussen, T.; Korall, B. Angew. Chem., Int. Ed. Engl. 1991, 30, 1312-1314.
23. Franke, R.; Rothe, J.; Pollmann, J.; Hormes, J.; Bönnemann, H.; Brijoux, W.; Hindenburg, T. J. Am. Chem. Soc. 1996, 118, 12090-12097.
24. 1a
25. Köhler, J.; Bradley, J. S. Catal. Lett. 1997, 45, 203-208.
26. Stoeva, S.; Klabunde, K. J.; Sornesen, C. M.; Dragieva, I. J. Am. Chem. Soc. 2002, 124, 2305-2311.
27. Chen, S.; Kimura, K. Langmuir 1999, 15, 1075-1082.
28. Yu, W.; Liu, H. Chem. Mater. 1999, 10, 1205.
29. (a) Yin, Y.; Li, Z.-Y.; Zhong, Z.; Gates, B.; Xia, Y.; Venkateswaran, S. Mater. Chem. 2002, 12, 552-527.
30. (b) Lu, L.; Wang, H.; Xi, S.; Zhang, H. J. Mater. Chem. 2002, 12, 156-158.
31. (c) Liao, X.-H.; Zhu, J.-M.; Zhu, J.-J.; Xu, J.-Z.; Chen, H.-Y. Chem. Commun. 2001, 937-938.
32. (d) Tu. W.; Liu, H. Chem. Mater. 2000, 12, 564-567.
33. (e) Oku, T.; Kusunose, T.; Niihara, K.; Suganuma, K. J. Mater. Chem. 2000, 10, 255-257.
34. (f) Sun, Y.-P.; Rollins, H. W.; Guduru, R. Chem. Mater. 1999, 11, 7-9.
35. 2 due to the formation of metal-oxide coatings.
36. (b) Kolb, U.; Quaiser, S. A.; Winter, M.; Reetz, M. T. Chem. Mater. 1996, 8, 1889-1894.
37. (c) Reetz, M. T.; Quaiser, S. A.; Winter, M.; Becker, J. A.; Schafer, R.; Stimming, U.; Marmann, A.; Vogel, R.; Konno, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 2092.
38. (d) Harada, M.; Asakura, K.; Ueki, Y.; Toshima, N. J. Phys. Chem. 1992, 96, 9730-9738.
39. (e) See also reference 20(c).
40. 2, by using a N2- filled drybox and sealed Fischer-Porter bottles that attach directly to the hydrogenation line via Swagelock quick-connects (see the Experimental Section).
41. (b) Hamlin, J. E.; Hirai, K.; Gibson, V. C.; Maitlis, P. M. J. Mol. Catal. 1982, 15, 337-347.
42. (c) Logan, A. D.; Sharoudi, K.; Datye, A. K. J. Phys. Chem. 1991, 95, 5568, and references therein.
43. 2 effects on metal-particle catalysis is given on p 175 of: Maxted, E. B. Adv. Catal. 1981, 3, 129-179.
44. Ceyer, S. T. Acc. Chem. Res. 2001, 34, 737-744.
45. Reports that assay nanocluster stability by solubility include the following: (a) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.; Nishihara, H. Langmuir 2002, 18, 1413-1418. (b) Zhou, Y.; Itoh, H.; Uemura, T.; Naka, K.; Chujo, Y. Langmuir 2002, 18, 277-283. (c) Kim, H. S.; Ryu, J. H.; Jose, B.; Lee, B. G.; Ahn, B. S.; Kang, Y. S. Langmuir 2001, 17, 5817-5820. (d) Yu, H.; Gibbons, P. C.; Kelton, K. F.; Buhro, W. E. J. Am. Chem. Soc. 2001,123, 9198-9199. (e) Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Jiao, J.; Seraphin, S. Angew. Chem., Int. Ed. Engl. 2001, 40, 549-552. (f) Yan, X.; Liu, H.; Liew, Y. J. Mater. Chem. 2001, 11, 3387-3391. (g) Teranishi, T.; Haga, M.; Shiozawa, Y.; Miyake, M. J. Am. Chem. Soc. 2000, 122, 4237-4238. (h) Yang, C.-S.; Liu, Q.; Kauzlarich, S. M.; Phillips, B. Chem. Mater. 2000, 12, 983-988. (i) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater. 2000, 12, 1622-1627. (j) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J.-O.; Bovin, J.-O.; Senocq, F.; Casanove, M.-J. Angew. Chem., Int. Ed. 1999, 38, 3736-3738. (k) Naka, K.; Yaguchi, M.; Chujo, Y. Chem. Mater. 1999, 11, 849 851. (l) Yonezawa, T.; Toshima, N.; J. Chem. Soc., Faraday Trans. 1995, 91, 4111-4119. (m) Lewis, L. N.; Lewis, N. Chem. Mater. 1989, 1, 106-114.
46. Reports that assay nanocluster stability by solubility include the following: (a) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.; Nishihara, H. Langmuir 2002, 18, 1413-1418. (b) Zhou, Y.; Itoh, H.; Uemura, T.; Naka, K.; Chujo, Y. Langmuir 2002, 18, 277-283. (c) Kim, H. S.; Ryu, J. H.; Jose, B.; Lee, B. G.; Ahn, B. S.; Kang, Y. S. Langmuir 2001, 17, 5817-5820. (d) Yu, H.; Gibbons, P. C.; Kelton, K. F.; Buhro, W. E. J. Am. Chem. Soc. 2001,123, 9198-9199. (e) Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Jiao, J.; Seraphin, S. Angew. Chem., Int. Ed. Engl. 2001, 40, 549-552. (f) Yan, X.; Liu, H.; Liew, Y. J. Mater. Chem. 2001, 11, 3387-3391. (g) Teranishi, T.; Haga, M.; Shiozawa, Y.; Miyake, M. J. Am. Chem. Soc. 2000, 122, 4237-4238. (h) Yang, C.-S.; Liu, Q.; Kauzlarich, S. M.; Phillips, B. Chem. Mater. 2000, 12, 983-988. (i) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater. 2000, 12, 1622-1627. (j) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J.-O.; Bovin, J.-O.; Senocq, F.; Casanove, M.-J. Angew. Chem., Int. Ed. 1999, 38, 3736-3738. (k) Naka, K.; Yaguchi, M.; Chujo, Y. Chem. Mater. 1999, 11, 849 851. (l) Yonezawa, T.; Toshima, N.; J. Chem. Soc., Faraday Trans. 1995, 91, 4111-4119. (m) Lewis, L. N.; Lewis, N. Chem. Mater. 1989, 1, 106-114.
47. Reports that assay nanocluster stability by solubility include the following: (a) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.; Nishihara, H. Langmuir 2002, 18, 1413-1418. (b) Zhou, Y.; Itoh, H.; Uemura, T.; Naka, K.; Chujo, Y. Langmuir 2002, 18, 277-283. (c) Kim, H. S.; Ryu, J. H.; Jose, B.; Lee, B. G.; Ahn, B. S.; Kang, Y. S. Langmuir 2001, 17, 5817-5820. (d) Yu, H.; Gibbons, P. C.; Kelton, K. F.; Buhro, W. E. J. Am. Chem. Soc. 2001,123, 9198-9199. (e) Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Jiao, J.; Seraphin, S. Angew. Chem., Int. Ed. Engl. 2001, 40, 549-552. (f) Yan, X.; Liu, H.; Liew, Y. J. Mater. Chem. 2001, 11, 3387-3391. (g) Teranishi, T.; Haga, M.; Shiozawa, Y.; Miyake, M. J. Am. Chem. Soc. 2000, 122, 4237-4238. (h) Yang, C.-S.; Liu, Q.; Kauzlarich, S. M.; Phillips, B. Chem. Mater. 2000, 12, 983-988. (i) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater. 2000, 12, 1622-1627. (j) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J.-O.; Bovin, J.-O.; Senocq, F.; Casanove, M.-J. Angew. Chem., Int. Ed. 1999, 38, 3736-3738. (k) Naka, K.; Yaguchi, M.; Chujo, Y. Chem. Mater. 1999, 11, 849 851. (l) Yonezawa, T.; Toshima, N.; J. Chem. Soc., Faraday Trans. 1995, 91, 4111-4119. (m) Lewis, L. N.; Lewis, N. Chem. Mater. 1989, 1, 106-114.
48. Reports that assay nanocluster stability by solubility include the following: (a) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.; Nishihara, H. Langmuir 2002, 18, 1413-1418. (b) Zhou, Y.; Itoh, H.; Uemura, T.; Naka, K.; Chujo, Y. Langmuir 2002, 18, 277-283. (c) Kim, H. S.; Ryu, J. H.; Jose, B.; Lee, B. G.; Ahn, B. S.; Kang, Y. S. Langmuir 2001, 17, 5817-5820. (d) Yu, H.; Gibbons, P. C.; Kelton, K. F.; Buhro, W. E. J. Am. Chem. Soc. 2001,123, 9198-9199. (e) Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Jiao, J.; Seraphin, S. Angew. Chem., Int. Ed. Engl. 2001, 40, 549-552. (f) Yan, X.; Liu, H.; Liew, Y. J. Mater. Chem. 2001, 11, 3387-3391. (g) Teranishi, T.; Haga, M.; Shiozawa, Y.; Miyake, M. J. Am. Chem. Soc. 2000, 122, 4237-4238. (h) Yang, C.-S.; Liu, Q.; Kauzlarich, S. M.; Phillips, B. Chem. Mater. 2000, 12, 983-988. (i) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater. 2000, 12, 1622-1627. (j) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J.-O.; Bovin, J.-O.; Senocq, F.; Casanove, M.-J. Angew. Chem., Int. Ed. 1999, 38, 3736-3738. (k) Naka, K.; Yaguchi, M.; Chujo, Y. Chem. Mater. 1999, 11, 849 851. (l) Yonezawa, T.; Toshima, N.; J. Chem. Soc., Faraday Trans. 1995, 91, 4111-4119. (m) Lewis, L. N.; Lewis, N. Chem. Mater. 1989, 1, 106-114.
49. Reports that assay nanocluster stability by solubility include the following: (a) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.; Nishihara, H. Langmuir 2002, 18, 1413-1418. (b) Zhou, Y.; Itoh, H.; Uemura, T.; Naka, K.; Chujo, Y. Langmuir 2002, 18, 277-283. (c) Kim, H. S.; Ryu, J. H.; Jose, B.; Lee, B. G.; Ahn, B. S.; Kang, Y. S. Langmuir 2001, 17, 5817-5820. (d) Yu, H.; Gibbons, P. C.; Kelton, K. F.; Buhro, W. E. J. Am. Chem. Soc. 2001,123, 9198-9199. (e) Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Jiao, J.; Seraphin, S. Angew. Chem., Int. Ed. Engl. 2001, 40, 549-552. (f) Yan, X.; Liu, H.; Liew, Y. J. Mater. Chem. 2001, 11, 3387-3391. (g) Teranishi, T.; Haga, M.; Shiozawa, Y.; Miyake, M. J. Am. Chem. Soc. 2000, 122, 4237-4238. (h) Yang, C.-S.; Liu, Q.; Kauzlarich, S. M.; Phillips, B. Chem. Mater. 2000, 12, 983-988. (i) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater. 2000, 12, 1622-1627. (j) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J.-O.; Bovin, J.-O.; Senocq, F.; Casanove, M.-J. Angew. Chem., Int. Ed. 1999, 38, 3736-3738. (k) Naka, K.; Yaguchi, M.; Chujo, Y. Chem. Mater. 1999, 11, 849 851. (l) Yonezawa, T.; Toshima, N.; J. Chem. Soc., Faraday Trans. 1995, 91, 4111-4119. (m) Lewis, L. N.; Lewis, N. Chem. Mater. 1989, 1, 106-114.
50. Reports that assay nanocluster stability by solubility include the following: (a) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.; Nishihara, H. Langmuir 2002, 18, 1413-1418. (b) Zhou, Y.; Itoh, H.; Uemura, T.; Naka, K.; Chujo, Y. Langmuir 2002, 18, 277-283. (c) Kim, H. S.; Ryu, J. H.; Jose, B.; Lee, B. G.; Ahn, B. S.; Kang, Y. S. Langmuir 2001, 17, 5817-5820. (d) Yu, H.; Gibbons, P. C.; Kelton, K. F.; Buhro, W. E. J. Am. Chem. Soc. 2001,123, 9198-9199. (e) Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Jiao, J.; Seraphin, S. Angew. Chem., Int. Ed. Engl. 2001, 40, 549-552. (f) Yan, X.; Liu, H.; Liew, Y. J. Mater. Chem. 2001, 11, 3387-3391. (g) Teranishi, T.; Haga, M.; Shiozawa, Y.; Miyake, M. J. Am. Chem. Soc. 2000, 122, 4237-4238. (h) Yang, C.-S.; Liu, Q.; Kauzlarich, S. M.; Phillips, B. Chem. Mater. 2000, 12, 983-988. (i) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater. 2000, 12, 1622-1627. (j) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J.-O.; Bovin, J.-O.; Senocq, F.; Casanove, M.-J. Angew. Chem., Int. Ed. 1999, 38, 3736-3738. (k) Naka, K.; Yaguchi, M.; Chujo, Y. Chem. Mater. 1999, 11, 849 851. (l) Yonezawa, T.; Toshima, N.; J. Chem. Soc., Faraday Trans. 1995, 91, 4111-4119. (m) Lewis, L. N.; Lewis, N. Chem. Mater. 1989, 1, 106-114.
51. Reports that assay nanocluster stability by solubility include the following: (a) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.; Nishihara, H. Langmuir 2002, 18, 1413-1418. (b) Zhou, Y.; Itoh, H.; Uemura, T.; Naka, K.; Chujo, Y. Langmuir 2002, 18, 277-283. (c) Kim, H. S.; Ryu, J. H.; Jose, B.; Lee, B. G.; Ahn, B. S.; Kang, Y. S. Langmuir 2001, 17, 5817-5820. (d) Yu, H.; Gibbons, P. C.; Kelton, K. F.; Buhro, W. E. J. Am. Chem. Soc. 2001,123, 9198-9199. (e) Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Jiao, J.; Seraphin, S. Angew. Chem., Int. Ed. Engl. 2001, 40, 549-552. (f) Yan, X.; Liu, H.; Liew, Y. J. Mater. Chem. 2001, 11, 3387-3391. (g) Teranishi, T.; Haga, M.; Shiozawa, Y.; Miyake, M. J. Am. Chem. Soc. 2000, 122, 4237-4238. (h) Yang, C.-S.; Liu, Q.; Kauzlarich, S. M.; Phillips, B. Chem. Mater. 2000, 12, 983-988. (i) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater. 2000, 12, 1622-1627. (j) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J.-O.; Bovin, J.-O.; Senocq, F.; Casanove, M.-J. Angew. Chem., Int. Ed. 1999, 38, 3736-3738. (k) Naka, K.; Yaguchi, M.; Chujo, Y. Chem. Mater. 1999, 11, 849 851. (l) Yonezawa, T.; Toshima, N.; J. Chem. Soc., Faraday Trans. 1995, 91, 4111-4119. (m) Lewis, L. N.; Lewis, N. Chem. Mater. 1989, 1, 106-114.
52. Reports that assay nanocluster stability by solubility include the following: (a) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.; Nishihara, H. Langmuir 2002, 18, 1413-1418. (b) Zhou, Y.; Itoh, H.; Uemura, T.; Naka, K.; Chujo, Y. Langmuir 2002, 18, 277-283. (c) Kim, H. S.; Ryu, J. H.; Jose, B.; Lee, B. G.; Ahn, B. S.; Kang, Y. S. Langmuir 2001, 17, 5817-5820. (d) Yu, H.; Gibbons, P. C.; Kelton, K. F.; Buhro, W. E. J. Am. Chem. Soc. 2001,123, 9198-9199. (e) Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Jiao, J.; Seraphin, S. Angew. Chem., Int. Ed. Engl. 2001, 40, 549-552. (f) Yan, X.; Liu, H.; Liew, Y. J. Mater. Chem. 2001, 11, 3387-3391. (g) Teranishi, T.; Haga, M.; Shiozawa, Y.; Miyake, M. J. Am. Chem. Soc. 2000, 122, 4237-4238. (h) Yang, C.-S.; Liu, Q.; Kauzlarich, S. M.; Phillips, B. Chem. Mater. 2000, 12, 983-988. (i) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater. 2000, 12, 1622-1627. (j) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J.-O.; Bovin, J.-O.; Senocq, F.; Casanove, M.-J. Angew. Chem., Int. Ed. 1999, 38, 3736-3738. (k) Naka, K.; Yaguchi, M.; Chujo, Y. Chem. Mater. 1999, 11, 849 851. (l) Yonezawa, T.; Toshima, N.; J. Chem. Soc., Faraday Trans. 1995, 91, 4111-4119. (m) Lewis, L. N.; Lewis, N. Chem. Mater. 1989, 1, 106-114.
53. Reports that assay nanocluster stability by solubility include the following: (a) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.; Nishihara, H. Langmuir 2002, 18, 1413-1418. (b) Zhou, Y.; Itoh, H.; Uemura, T.; Naka, K.; Chujo, Y. Langmuir 2002, 18, 277-283. (c) Kim, H. S.; Ryu, J. H.; Jose, B.; Lee, B. G.; Ahn, B. S.; Kang, Y. S. Langmuir 2001, 17, 5817-5820. (d) Yu, H.; Gibbons, P. C.; Kelton, K. F.; Buhro, W. E. J. Am. Chem. Soc. 2001,123, 9198-9199. (e) Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Jiao, J.; Seraphin, S. Angew. Chem., Int. Ed. Engl. 2001, 40, 549-552. (f) Yan, X.; Liu, H.; Liew, Y. J. Mater. Chem. 2001, 11, 3387-3391. (g) Teranishi, T.; Haga, M.; Shiozawa, Y.; Miyake, M. J. Am. Chem. Soc. 2000, 122, 4237-4238. (h) Yang, C.-S.; Liu, Q.; Kauzlarich, S. M.; Phillips, B. Chem. Mater. 2000, 12, 983-988. (i) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater. 2000, 12, 1622-1627. (j) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J.-O.; Bovin, J.-O.; Senocq, F.; Casanove, M.-J. Angew. Chem., Int. Ed. 1999, 38, 3736-3738. (k) Naka, K.; Yaguchi, M.; Chujo, Y. Chem. Mater. 1999, 11, 849 851. (l) Yonezawa, T.; Toshima, N.; J. Chem. Soc., Faraday Trans. 1995, 91, 4111-4119. (m) Lewis, L. N.; Lewis, N. Chem. Mater. 1989, 1, 106-114.
54. Reports that assay nanocluster stability by solubility include the following: (a) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.; Nishihara, H. Langmuir 2002, 18, 1413-1418. (b) Zhou, Y.; Itoh, H.; Uemura, T.; Naka, K.; Chujo, Y. Langmuir 2002, 18, 277-283. (c) Kim, H. S.; Ryu, J. H.; Jose, B.; Lee, B. G.; Ahn, B. S.; Kang, Y. S. Langmuir 2001, 17, 5817-5820. (d) Yu, H.; Gibbons, P. C.; Kelton, K. F.; Buhro, W. E. J. Am. Chem. Soc. 2001,123, 9198-9199. (e) Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Jiao, J.; Seraphin, S. Angew. Chem., Int. Ed. Engl. 2001, 40, 549-552. (f) Yan, X.; Liu, H.; Liew, Y. J. Mater. Chem. 2001, 11, 3387-3391. (g) Teranishi, T.; Haga, M.; Shiozawa, Y.; Miyake, M. J. Am. Chem. Soc. 2000, 122, 4237-4238. (h) Yang, C.-S.; Liu, Q.; Kauzlarich, S. M.; Phillips, B. Chem. Mater. 2000, 12, 983-988. (i) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater. 2000, 12, 1622-1627. (j) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J.-O.; Bovin, J.-O.; Senocq, F.; Casanove, M.-J. Angew. Chem., Int. Ed. 1999, 38, 3736-3738. (k) Naka, K.; Yaguchi, M.; Chujo, Y. Chem. Mater. 1999, 11, 849 851. (l) Yonezawa, T.; Toshima, N.; J. Chem. Soc., Faraday Trans. 1995, 91, 4111-4119. (m) Lewis, L. N.; Lewis, N. Chem. Mater. 1989, 1, 106-114.
55. Reports that assay nanocluster stability by solubility include the following: (a) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.; Nishihara, H. Langmuir 2002, 18, 1413-1418. (b) Zhou, Y.; Itoh, H.; Uemura, T.; Naka, K.; Chujo, Y. Langmuir 2002, 18, 277-283. (c) Kim, H. S.; Ryu, J. H.; Jose, B.; Lee, B. G.; Ahn, B. S.; Kang, Y. S. Langmuir 2001, 17, 5817-5820. (d) Yu, H.; Gibbons, P. C.; Kelton, K. F.; Buhro, W. E. J. Am. Chem. Soc. 2001,123, 9198-9199. (e) Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Jiao, J.; Seraphin, S. Angew. Chem., Int. Ed. Engl. 2001, 40, 549-552. (f) Yan, X.; Liu, H.; Liew, Y. J. Mater. Chem. 2001, 11, 3387-3391. (g) Teranishi, T.; Haga, M.; Shiozawa, Y.; Miyake, M. J. Am. Chem. Soc. 2000, 122, 4237-4238. (h) Yang, C.-S.; Liu, Q.; Kauzlarich, S. M.; Phillips, B. Chem. Mater. 2000, 12, 983-988. (i) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater. 2000, 12, 1622-1627. (j) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J.-O.; Bovin, J.-O.; Senocq, F.; Casanove, M.-J. Angew. Chem., Int. Ed. 1999, 38, 3736-3738. (k) Naka, K.; Yaguchi, M.; Chujo, Y. Chem. Mater. 1999, 11, 849 851. (l) Yonezawa, T.; Toshima, N.; J. Chem. Soc., Faraday Trans. 1995, 91, 4111-4119. (m) Lewis, L. N.; Lewis, N. Chem. Mater. 1989, 1, 106-114.
56. Reports that assay nanocluster stability by solubility include the following: (a) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.; Nishihara, H. Langmuir 2002, 18, 1413-1418. (b) Zhou, Y.; Itoh, H.; Uemura, T.; Naka, K.; Chujo, Y. Langmuir 2002, 18, 277-283. (c) Kim, H. S.; Ryu, J. H.; Jose, B.; Lee, B. G.; Ahn, B. S.; Kang, Y. S. Langmuir 2001, 17, 5817-5820. (d) Yu, H.; Gibbons, P. C.; Kelton, K. F.; Buhro, W. E. J. Am. Chem. Soc. 2001,123, 9198-9199. (e) Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Jiao, J.; Seraphin, S. Angew. Chem., Int. Ed. Engl. 2001, 40, 549-552. (f) Yan, X.; Liu, H.; Liew, Y. J. Mater. Chem. 2001, 11, 3387-3391. (g) Teranishi, T.; Haga, M.; Shiozawa, Y.; Miyake, M. J. Am. Chem. Soc. 2000, 122, 4237-4238. (h) Yang, C.-S.; Liu, Q.; Kauzlarich, S. M.; Phillips, B. Chem. Mater. 2000, 12, 983-988. (i) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater. 2000, 12, 1622-1627. (j) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J.-O.; Bovin, J.-O.; Senocq, F.; Casanove, M.-J. Angew. Chem., Int. Ed. 1999, 38, 3736-3738. (k) Naka, K.; Yaguchi, M.; Chujo, Y. Chem. Mater. 1999, 11, 849 851. (l) Yonezawa, T.; Toshima, N.; J. Chem. Soc., Faraday Trans. 1995, 91, 4111-4119. (m) Lewis, L. N.; Lewis, N. Chem. Mater. 1989, 1, 106-114.
57. Reports that assay nanocluster stability by solubility include the following: (a) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.; Nishihara, H. Langmuir 2002, 18, 1413-1418. (b) Zhou, Y.; Itoh, H.; Uemura, T.; Naka, K.; Chujo, Y. Langmuir 2002, 18, 277-283. (c) Kim, H. S.; Ryu, J. H.; Jose, B.; Lee, B. G.; Ahn, B. S.; Kang, Y. S. Langmuir 2001, 17, 5817-5820. (d) Yu, H.; Gibbons, P. C.; Kelton, K. F.; Buhro, W. E. J. Am. Chem. Soc. 2001,123, 9198-9199. (e) Wang, R.; Yang, J.; Zheng, Z.; Carducci, M. D.; Jiao, J.; Seraphin, S. Angew. Chem., Int. Ed. Engl. 2001, 40, 549-552. (f) Yan, X.; Liu, H.; Liew, Y. J. Mater. Chem. 2001, 11, 3387-3391. (g) Teranishi, T.; Haga, M.; Shiozawa, Y.; Miyake, M. J. Am. Chem. Soc. 2000, 122, 4237-4238. (h) Yang, C.-S.; Liu, Q.; Kauzlarich, S. M.; Phillips, B. Chem. Mater. 2000, 12, 983-988. (i) Wang, Y.; Ren, J.; Deng, K.; Gui, L.; Tang, Y. Chem. Mater. 2000, 12, 1622-1627. (j) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J.-O.; Bovin, J.-O.; Senocq, F.; Casanove, M.-J. Angew. Chem., Int. Ed. 1999, 38, 3736-3738. (k) Naka, K.; Yaguchi, M.; Chujo, Y. Chem. Mater. 1999, 11, 849 851. (l) Yonezawa, T.; Toshima, N.; J. Chem. Soc., Faraday Trans. 1995, 91, 4111-4119. (m) Lewis, L. N.; Lewis, N. Chem. Mater. 1989, 1, 106-114.
58. Özkar, S.; Finke, R. G. J. Am. Chem. Soc. 2002, 124, 5796-5810.
59. Reetz and co-workers were the first to report that propylene carbonate might be a preferred solvent for stabilizing nanoclusters: Reetz, M. T.; Lohmer, G. J. Chem. Soc., Chem. Commun. 1996, 1921-1922.
60. Fundamental studies are underway, using the methods and five criteria recently developed, examining the relative ability of solvents of high dielectric constant such as propylene carbonate and N-methylacetamide for their ability to stabilize transition-metal nanoclusters: Starkey, L.; Finke, R. G., unpublished results and experiments in progress.
61. Samples for TEM analysis were prepared according to our previously published procedure: Widegren, J. A.; Finke, R. G. Inorg. Chem. 2002, 41, 1558-1572.
62. (a) Yonezawa, T.; Onoue, S.-Y.; Kimizuka, N. Adv. Mater. 2001, 13, 140-142.
63. (b) Yonezawa, T.; Yasui, K.; Kimizuka, N. Langmiur 2001, 17, 271-273.
64. (c) Perez, H.; Pradeau, J.-P.; Albouy, P.-A.; Perez-Omil, J. Chem. Mater. 1999, 11, 3460-3463.
65. Hornstein, B. J.; Aiken, J. D., III; Finke, R. G. Inorg. Chem. 2002, 41, 1625-1638.
66. Boudart, M. Chem. Rev. 1995, 95, 661-666. Boudart, M. J. Mol. Catal. 1985, 30, 27.
67. Boudart, M. Chem. Rev. 1995, 95, 661-666. Boudart, M. J. Mol. Catal. 1985, 30, 27.
68. 28 one calculates that 35-40% of the exposed Ir(0) is active.
69. de Caro, D.; Bradley, J. S. New J. Chem. 1998, 22, 1267-1273.
70. 32b
71. Based on a chapter in Jason A. Widegren's Ph.D. dissertation, Colorado State University, Aug 2002.
72. Aiken, J. D., III; Finke R. G. J. Am. Chem. Soc. 1998, 120, 9545-9554.
73. 2Ir(0) stoichiometry is 1/1.
74. Watzky, M. A.; Finke, R. G. Chem. Mater, 1997, 9, 3083.
75. Nieuwenhuys, B. E.; Somorjai, G. A. Surf. Sci. 1978, 72, 8-32.
76. Berkó, A.; Solymosi, F. J. Phys. Chem. B 2000, 104, 10215-10221.
77. 38a,c-e have been used to assess the stability of transition-metal nanoclusters. (a) Tzhayik, O.; Sawant, P.; Efrima, S.; Kovalev, E.; Klug, J. T. Langmiur 2002, 18, 3364-3369. (b) Zhao, S.-Y.; Chen, S.-H.; Wang, S.-Y.; Li, D.-G.; Ma, H.-Y. Langmiur 2002, 18, 3315-3318. (c) Pastoriza-Santos, I.; Liz-Marzan, L. M. Langmiur 2002, 18, 2888-2894. (d) Walker, C. H.; St. John, J. V.; Wisian-Neilson, P. J. Am. Chem. Soc. 2001, 123, 3846-3847. (e) Zhang, Z.; Patel. R. C.; Kothari, R.; Johnson, C. P.; Friberg, S. E.; Aikens, P. A. J. Phys. Chem. B 2000, 104, 1176-1182.
78. 38a,c-e have been used to assess the stability of transition-metal nanoclusters. (a) Tzhayik, O.; Sawant, P.; Efrima, S.; Kovalev, E.; Klug, J. T. Langmiur 2002, 18, 3364-3369. (b) Zhao, S.-Y.; Chen, S.-H.; Wang, S.-Y.; Li, D.-G.; Ma, H.-Y. Langmiur 2002, 18, 3315-3318. (c) Pastoriza-Santos, I.; Liz-Marzan, L. M. Langmiur 2002, 18, 2888-2894. (d) Walker, C. H.; St. John, J. V.; Wisian-Neilson, P. J. Am. Chem. Soc. 2001, 123, 3846-3847. (e) Zhang, Z.; Patel. R. C.; Kothari, R.; Johnson, C. P.; Friberg, S. E.; Aikens, P. A. J. Phys. Chem. B 2000, 104, 1176-1182.
79. 38a,c-e have been used to assess the stability of transition-metal nanoclusters. (a) Tzhayik, O.; Sawant, P.; Efrima, S.; Kovalev, E.; Klug, J. T. Langmiur 2002, 18, 3364-3369. (b) Zhao, S.-Y.; Chen, S.-H.; Wang, S.-Y.; Li, D.-G.; Ma, H.-Y. Langmiur 2002, 18, 3315-3318. (c) Pastoriza-Santos, I.; Liz-Marzan, L. M. Langmiur 2002, 18, 2888-2894. (d) Walker, C. H.; St. John, J. V.; Wisian-Neilson, P. J. Am. Chem. Soc. 2001, 123, 3846-3847. (e) Zhang, Z.; Patel. R. C.; Kothari, R.; Johnson, C. P.; Friberg, S. E.; Aikens, P. A. J. Phys. Chem. B 2000, 104, 1176-1182.
80. 38a,c-e have been used to assess the stability of transition-metal nanoclusters. (a) Tzhayik, O.; Sawant, P.; Efrima, S.; Kovalev, E.; Klug, J. T. Langmiur 2002, 18, 3364-3369. (b) Zhao, S.-Y.; Chen, S.-H.; Wang, S.-Y.; Li, D.-G.; Ma, H.-Y. Langmiur 2002, 18, 3315-3318. (c) Pastoriza-Santos, I.; Liz-Marzan, L. M. Langmiur 2002, 18, 2888-2894. (d) Walker, C. H.; St. John, J. V.; Wisian-Neilson, P. J. Am. Chem. Soc. 2001, 123, 3846-3847. (e) Zhang, Z.; Patel. R. C.; Kothari, R.; Johnson, C. P.; Friberg, S. E.; Aikens, P. A. J. Phys. Chem. B 2000, 104, 1176-1182.
81. 38a,c-e have been used to assess the stability of transition-metal nanoclusters. (a) Tzhayik, O.; Sawant, P.; Efrima, S.; Kovalev, E.; Klug, J. T. Langmiur 2002, 18, 3364-3369. (b) Zhao, S.-Y.; Chen, S.-H.; Wang, S.-Y.; Li, D.-G.; Ma, H.-Y. Langmiur 2002, 18, 3315-3318. (c) Pastoriza-Santos, I.; Liz-Marzan, L. M. Langmiur 2002, 18, 2888-2894. (d) Walker, C. H.; St. John, J. V.; Wisian-Neilson, P. J. Am. Chem. Soc. 2001, 123, 3846-3847. (e) Zhang, Z.; Patel. R. C.; Kothari, R.; Johnson, C. P.; Friberg, S. E.; Aikens, P. A. J. Phys. Chem. B 2000, 104, 1176-1182.
82. The in situ stability of polymer-protected Ni/Pd bimetallic nanoclusters in the following study was tested by nitrobenzene hydrogenation activity: Lu, P.; Teranishi, T.; Asakura, K.; Miyake, M.; Toshima, N. J. Phys. Chem. B 1999, 103, 9673-9682.
83. 2 as a part of those studies: Toshima, N.; Shiraishi, Y.; Teranishi, T.; Miyake, M.; Tominaga, T.; Watanabe, H.; Brijoux, W.; Bönnemman, H.; Schmid, G. Appl. Organomet. Chem. 2001, 15, 178.
84. 2 as a part of those studies: Toshima, N.; Shiraishi, Y.; Teranishi, T.; Miyake, M.; Tominaga, T.; Watanabe, H.; Brijoux, W.; Bönnemman, H.; Schmid, G. Appl. Organomet. Chem. 2001, 15, 178.
85. 2 as a part of those studies: Toshima, N.; Shiraishi, Y.; Teranishi, T.; Miyake, M.; Tominaga, T.; Watanabe, H.; Brijoux, W.; Bönnemman, H.; Schmid, G. Appl. Organomet. Chem. 2001, 15, 178.
86. 2 as a part of those studies: Toshima, N.; Shiraishi, Y.; Teranishi, T.; Miyake, M.; Tominaga, T.; Watanabe, H.; Brijoux, W.; Bönnemman, H.; Schmid, G. Appl. Organomet. Chem. 2001, 15, 178.
87. 2 as a part of those studies: Toshima, N.; Shiraishi, Y.; Teranishi, T.; Miyake, M.; Tominaga, T.; Watanabe, H.; Brijoux, W.; Bönnemman, H.; Schmid, G. Appl. Organomet. Chem. 2001, 15, 178.
88. 2 as a part of those studies: Toshima, N.; Shiraishi, Y.; Teranishi, T.; Miyake, M.; Tominaga, T.; Watanabe, H.; Brijoux, W.; Bönnemman, H.; Schmid, G. Appl. Organomet. Chem. 2001, 15, 178.
89. n. hydrogenation catalysis).
90. Wieckowski, A.; Rosasco, S. D.; Salaita, G. N.; Hubbard, A.; Bent, B. E.; Zaera, F.; Godbey, D.; Somorjai, G. A. J. Am. Chem. Soc. 1985, 107, 5910-5920.
91. (a) Ferri, D.; Bürgi, T.; Baiker, A. J. Phys. Chem. B 2001, 105, 3187-3195.
92. (b) Choukroun, R.; de Caro, D.; Chaudret, B.; Lecante, P.; Snoeck, E. New J. Chem. 2001, 25, 525-527.
93. (c) Teeter, G.; Hinson, D.; Erskine, J. L. Phys. Rev. B 1998, 57, 4073-4080.
94. (d) Arnold, M.; Sologub, S.; Frie, W.; Hammer, L.; Heinz, K. J. Phys. Condens. Matter 1997, 9, 6481-6491.
95. (e) Tománek, D.; Wilke, S.; Scheffler, M. Phys. Rev. Lett. 1997, 79, 1329-1332.
96. (f) Somorjai, G. A. Annu. Rev. Phys. Chem. 1994, 45, 721-751.
97. (g) Hydrogen Effects in Catalysis: Fundamentals and Practical Applications; Paál, Z., Menon, P. G., Eds.; Marcel Dekker: New York, 1988.
98. nd ed.; Wiley-VCH: New York, 1999.
99. Widegren, J. A.; Aiken, J. D., III; Ozkar, S.; Finke, R. G. Chem. Mater. 2001, 13, 312-324.
100. (a) Stacchiola, D.; Azad, S.; Burkholder, L.; Tysoe, W. T. J. Phys. Chem. B 2001, 105, 11233-11239.
101. (b) Jacobs, P. W.; Somorjai, G. A. J. Mol. Catal. A 1998, 131, 5-18.
102. (c) Zaera, F. Langmuir 1996, 12, 88-94.
103. (d) Somorjai, G. A. Surface chemistry on the nanometer scale. Proc. Robert A. Welch Found. Conf. Chem. Res. 1996, 40, 57-85.
104. Argo, M. A.; Odzak, J. F.; Lai, F. S.; Gates, B. C. Nature 2002, 415, 623.
105. Lyon, D. K.; Aiken, J. D., III; Finke, R. G. Unpublished results.
106. Weiner, H.; Aiken, J. D., III; Finke, R. G. Inorg. Chem. 1996, 35, 7905-7913.
107. Hornstein, B. J.; Finke, R. G. Inorg. Chem. 2002, 41, 2720-2730.
108. Pohl, M.; Lyon, D. K.; Mizuno, N.; Nomiya, K.; Finke, R. G. Inorg. Chem. 1995, 34, 1413.
109. Aiken, J. D., III; Finke, R. G. Chem. Mater. 1999, 11, 1035-1047.
110. For evidence suggesting that heterogeneous nucleation can be a faster, lower energy pathway, at least in nanocluster formation reactions proceeding by diffusion-controlled steps, see: Strey, R.; Wagner, P. E.; Viisanen, Y. J. Phys. Chem. 1994, 98, 7748.
111. (a) Pope, M. T. Heteroply and Isopoly Oxometalates; Springer-Verlag: New York, 1983.
112. (b) Pope, M. T. Mixed-Valence Compounds; Brown, D. B., Ed.; Reidel: Dordrecht, The Netherlands, 1980.
113. (c) Buckley, R. I.; Clark, R. J. H. Coord. Chem. Rev. 1985, 65, 167.
114. 45).
115. Wilkins, R. G. Kinetics and Mechanism of Reactions of Transition Metal Complexes, 2nd ed.; VCH: New York, 1991.