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References 215 islands were observed (see above). It is also worth mentioning that, although there is clear preference for lines to grow along the edge of a dimer row, occasionally double lines are observed suggesting that hydrogen atom abstraction across a dimer row is also possible (separation of silicon atoms within a dimer is 2.34 A ˚ ). Abstraction across a single dimer has not been observed and is likely to be a prohibitively strained process (separation of silicon atoms on either edge is 5.34 A ˚ ) [46]. 8.5.5 SOME EXAMPLES OF TAILORED EXPERIMENTS ON MONOLAYERS Organic monolayers bonded to silicon in order to be of significant utility often require chemical functionality other than the methyl groups that terminate the most easily prepared monolayers of alkyl chains. The use of a, v-derivatized long-chain hydrocarbons has been a successful methodology, although not all functional groups are compatible for this purpose. For example, the reaction of Si(111) with 11-bromo-1-undecene has been used to prepare the anchor w (CH2) 11Br on the surface. Then, end-grafted polysilanes have been synthesized by reaction of polysilane having a silyl anion at the terminus with the bromoalkyl group [69]. This end-graft technique, gave the opportunity for direct AFM observation of polysilane single-molecule structures and allowed the physical properties of isolated polysilane chains to be measured. Another example is the reaction of Si(111) with ethyl undecylenate to afford the anchor w (CH2) 10C(O)OEt on the surface. Then, the ester groups were converted into di(2-thienyl)carbinol moieties by reaction with 2-thienyllithium and subsequently photoanodically oxidized in the presence of thiophene to yield a strongly adherent and smooth conducting film [70]. It is also worth mentioning that monolayers prepared from 1-octadecene on Si(111) were found to undergo chlorination exclusively on the terminal methyl group, when exposed to Cl2 with illumination at 350 nm [71]. This unusual high selectivity of radical chlorination demonstrates a strong steric effect due to the densely packed array of alkyl chains that favors attack at the chain ends. Other free radical reactions are expected to be convenient ways to functionalize methyl-terminated alkyl monolayers. 8.6 REFERENCES 1. West, R., J. Organomet. Chem., 1986, 300, 327. 2. Miller, R.D., and Michl, J., Chem. Rev., 1989, 89, 1359. 3. West, R. In The Chemistry of Organic Silicon Compounds, Volume 3, Z. Rappoport and Y. Apeloig (Eds), Wiley, Chichester, 2001, pp. 541–563. 4. Koe, J.R., and Fujiki, M., Silicon Chem., 2002, 1, 77. 5. Harrod, J.F., Prog. Catal., 1992, 147.
216 Silyl Radicals in Polymers and Materials 6. Tilley, T.D., Acc. Chem. Res., 1993, 26, 22. 7. Yamashita, H., and Tanaka, M., Bull. Chem. Soc. Jpn., 1995, 68, 403. 8. Banovetz, J.P., Suzuki, H., and Waymouth, R.M., Organometallics, 1993, 12, 4700. 9. Woo, H-G., Kim, S-Y., Han, M-K., Cho, E.J., and Jung, I.N., Organometallics, 1995, 14, 2415. 10. Banovetz, J.P., Stein, K.M., and Waymouth, R.M., Organometallics, 1991, 10, 3430. 11. Grimmond, B.J., Rath, N.P., and Corey, J.Y., Organometallics, 2000, 19, 2975. 12. Chatgilialoglu, C. Unpublished results. 13. Chatgilialoglu, C., Ferreri, C., Vecchi, D., Lucarini, M., and Pedulli, G.F., J. Organomet. Chem., 1997, 545/546, 475. 14. McKinley, A.J., Karatsu, T., Wallraff, G.M., Thompson, D.P., Miller, R.D., and Michl, J., J. Am. Chem. Soc., 1991, 113, 2003. 15. Chatgilialoglu, C., Guerrini, A., Lucarini, M., Pedulli, G.F., Carrozza, P., Da Roit, G., Borzatta, V., and Lucchini, V., Organometallics, 1998, 17, 2169. 16. Zaborovskiy, A.B., Timokhin, V.I., and Chatgilialoglu, C., Polym. Sci., Series A, 2003, 45, 612. 17. Chatgilialoglu, C., Timokhin, V.I., Zaborovskiy, A.B., Lutsyk, D.A., and Prystansky, R.E., J. Chem. Soc., Perkin Trans. 2, 2000, 577. 18. Chatgilialoglu, C., Guarini, A., Guerrini, A., and Seconi, G., J. Org. Chem., 1992, 57, 2207. 19. Zaborovskiy, A.B., Lutsyk, D.A., Prystansky, R.E., Kopylets, V.I., Timokhin, V.I., and Chatgilialoglu, C., Unpublished results. 20. Pratt, D.A., DiLabio, G.A., Brigati, G., Pedulli, G.F., and Valgimigli, L., J. Am. Chem. Soc., 2001, 123, 4625. 21. Banovetz, J.P., Hsiao, Y-L., and Waymouth, R.M., J. Am. Chem. Soc., 1993, 115, 2540. 22. Hsiao, Y-L., Banovetz, J.P., and Waymouth, R.M., ACS Symp. Ser., 1994, 572, 55. 23. Hsiao, Y-L., and Waymouth, R.M., J. Am. Chem. Soc., 1994, 116, 9779. 24. Beach, J.V., Loy, D.A., Hsiao, Y-L., and Waymouth, R.M., Polym. Prepr., (Am. Chem. Soc., Div. Polym. Chem.), 1995, 72, 205. 25. For the use of poly(hydrosilane)s as process stabilizers, see: Carrozza, P., Borzatta, V., Chatgilialoglu, C. PCT Int. Appl. WO97/02322, 1997; U.S. patent 6005036, 1999; EP patent 836635, 2001. 26. For the use of polysilane stabilizers containing sterically hindered amine groups, see: Carrozza, P., Borzatta, V., Chatgilialoglu, C., and Da Roit, G. PCT Int. Appl. WO00/64965, 2000; US patent 6538055, 2003; EP patent 1185577, 2003. 27. Hirsch, A., Fullerenes and Related Structures, Springer, Berlin, 1998. 28. Wang, Y., West, R., Yuan, and C.-H., J. Am. Chem. Soc., 1993, 115, 3844. 29. Keizer, P.N., Morton, J.R., Preston, K.F., and Krusic, P.J., J. Chem. Soc., Perkin Trans. 2, 1993, 1041. 30. Kusukawa T., and Ando, W., Organometallics, 1997, 16, 4027. 31. Kusukawa K., and Ando, W., J. Organomet. Chem., 1998, 559, 11. 32. Akasaka, T., Suzuki, T., Maeda, Y., Ara, M., Wakahara, T., Kobayashi, K., Nagase, S., Kako, M., Nakadaira, Y., Fujitsuka M., and Ito, O., J. Org. Chem., 1999, 64, 566. 33. Kusukawa K., and Ando, W., Angew. Chem. Int. Ed. Engl., 1996, 35, 1315. 34. Ando, W., and Kusukawa K. In The Chemistry of Organic Silicon Compounds, Volume 2, Z. Rappoport and Y. Apeloig (Eds), Wiley, Chichester, 1998, pp. 1929– 1960. 35. Wakahara, T., Kondo, T., Okamura, M., Akasaka, T., Hamada, Y., Suzuki, T., Kako, M., and Nakadaira, Y., J. Organomet. Chem., 2000, 611, 78. 36. Watanabe, A., and Ito, O., J. Phys. Chem., 1994, 98, 7736.
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Organosilanes in Radical Chemistry
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DEDICATION To my parents XrZstoB an
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viii Contents 3.6 Hydrogen Atom: An
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PREFACE A large number of papers de
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ACKNOWLEDGEMENTS I thank Keith U. I
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2 Formation and Structures of Silyl
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10 Formation and Structures of Sily
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2 Thermochemistry 2.1 GENERAL CONSI
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Bond Dissociation Enthalpies 21 Tab
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Bond Dissociation Enthalpies 23 2.2
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Ion Thermochemistry 25 Table 2.4 Re
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Ion Thermochemistry 27 Table 2.5 El
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References 29 3. Goumri, A., Yuan,
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32 Hydrogen Donor Abilities of Sili
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4 Reducing Agents 4.1 GENERAL ASPEC
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General Aspects of Radical Chain Re
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Tris(trimethylsilyl)silane 53 Therm
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Tris(trimethylsilyl)silane 55 4.3.1
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Tris(trimethylsilyl)silane 57 A goo
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Tris(trimethylsilyl)silane 59 C(O)C
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Tris(trimethylsilyl)silane 61 radic
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Tris(trimethylsilyl)silane 63 86% y
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Tris(trimethylsilyl)silane 65 RO RO
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Tris(trimethylsilyl)silane 67 O AcO
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Tris(trimethylsilyl)silane 69 Tris(
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Other Silicon Hydrides 71 The reduc
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Other Silicon Hydrides 73 The decre
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Other Silicon Hydrides 75 Ph MeS O
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Other Silicon Hydrides 77 Table 4.6
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Silicon Hydride / Thiol Mixture 79
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Silylated Cyclohexadienes 81 and (4
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References 83 34. Kawashima, E., Uc
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References 85 104. Gimisis, T., Bal
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88 Addition to Unsaturated Bonds te
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90 Addition to Unsaturated Bonds ap
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92 Addition to Unsaturated Bonds 5.
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94 Addition to Unsaturated Bonds R
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96 Addition to Unsaturated Bonds Ph
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98 Addition to Unsaturated Bonds EP
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100 Addition to Unsaturated Bonds 5
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102 Addition to Unsaturated Bonds T
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104 Addition to Unsaturated Bonds R
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106 Addition to Unsaturated Bonds a
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110 Addition to Unsaturated Bonds S
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112 Addition to Unsaturated Bonds T
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114 Addition to Unsaturated Bonds I
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120 Unimolecular Reactions 1 Si(H)M
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122 Unimolecular Reactions t-Bu t-B
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124 Unimolecular Reactions MeO Si O
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126 Unimolecular Reactions t-Bu t-B
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128 Unimolecular Reactions R 1 R 2
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130 Unimolecular Reactions From the
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132 Unimolecular Reactions rearrang
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134 Unimolecular Reactions H 3 C +
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136 Unimolecular Reactions Br O Si(
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138 Unimolecular Reactions R3Si C C
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140 Unimolecular Reactions Me3Si O
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142 Unimolecular Reactions 43. Albe
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144 Consecutive Radical Reactions c
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146 Consecutive Radical Reactions O
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148 Consecutive Radical Reactions a
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150 Consecutive Radical Reactions d
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152 Consecutive Radical Reactions T
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154 Consecutive Radical Reactions M
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156 Consecutive Radical Reactions F
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162 Consecutive Radical Reactions i
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Page 191 and 192: 186 Silyl Radicals in Polymers and
Page 219: 214 Silyl Radicals in Polymers and
Page 225 and 226: 220 List of Abbreviations PED photo
Page 227 and 228: 222 Index Carbonyl sulfide 111 Carb
Page 229 and 230: 224 Index Organosilicon boranes 2,
Page 231 and 232: 226 Index Triethylsilane as mediato
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