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28 Thermochemistry Table 2.6 Gas-phase basicities of silanes and adiabatic ionization potential of silyl radicals a Silane (R3SiH) DHbase(R3Si w H) b (kJ/mol) IP(R3Si:) c (eV) H3Si w H 1094 8:11 d MeSiH2 w H 1029 7.40 Me2SiH w H 963 6.67 Me3Si w H 923 6.20 PhSiH2 w H 962 6.81 a From References [30,31]. b Estimated errors 4kJ=mol. c Calculated using Equation (2.16). d A value of 8:14 0:01 eV is obtained from the photoelectron spectrum [32]. Ion cyclotron resonance (ICR) spectroscopy has been used to determine the reaction enthalphy (DHr) of hydride-transfer reaction of silanes with various hydrocarbons having known hydride affinities (Reaction 2.19). The hydride affinities of R3Siþ , DH(X3Siþ w H ) ¼ DHbase, were obtained from Equation (2.20) and are summarized in Table 2.6 [30,31]. R3SiH þ X3C þ Ð R3Si þ þ X3CH (2:19) DH(R3Si þ þ H ) ¼ DH(X3C H ) þ DHr (2:20) w w The adiabatic ionization potentials of substituted silyl radicals, shown in Table 2.6, were recalculated from Equation (2.18) by using the appropriate DHbase and DH(R3Si H) values together with the EA(H:) ¼ 0:754 eV. Re- w placement of hydrogen by a methyl or phenyl group decreases the IP by 0:7 and 1:3 eV, respectively. Moreover, the first and second methyl substitutions decrease the IP by an equal amount, the third being significantly less. Other positive-ion cycles can afford complementary data related to the two dissociation paths of radical cation R3Siþ: (Scheme 2.1). Considering the Si H bond dissociation of PhSiH w þ: 3 as an example (Reaction 2.21), the thermochemical cycle in Equation (2.22) links the gas-phase basicity of silane (DHbase) to the DH(PhSiH þ: 3 ). Taking IP(PhSiH3) ¼ 9:09 eV [31], a bond strength of 159 kJ/mol is calculated. PhSiH þ: 3 !PhSiHþ 2 þ H: (2:21) DH(PhSiH þ: 3 ) ¼ DHbase(PhSiH3) þ EA(H:) IP(PhSiH3) (2:22) 2.4 REFERENCES 1. Chatgilialoglu, C., Chem. Rev., 1995, 95, 1229. 2. Seetula, J.A., Feng, Y., Gutman, D., Seakins, P.W., and Pilling, M.J., J. Chem. Phys., 1991, 95, 1658.
References 29 3. Goumri, A., Yuan, W.-J., and Marshall, P., J. Am. Chem. Soc., 1993, 115, 2539. Kalinovski, I.J., Gutman, D., Krasnoperov, L.N., Goumri, A., Yuan, W.-J., Marshall, P., J. Chem. Phys., 1994, 98, 9551. 4. Ding, L., and Marshall, P., J. Chem. Soc., Faraday Trans., 1993, 89, 419. 5. Becerra, R., and Walsh, R. In The Chemistry of Organic Silicon Compounds, Z. Rappoport, and Y. Apeloig, (Eds), Wiley, Chichester, 1998, Chapter 4, pp. 153–180. 6. Bullock, W.J., Walsh, R., and King, K.D., J. Phys. Chem., 1994, 98, 2595. 7. Berkowitz, J., Ellison, G.B., and Gutman, D., J. Phys. Chem., 1994, 98, 2744. 8. Laarhoven, L.J.J., Mulder, P., and Wayner, D.D.M., Acc. Chem. Res., 1999, 32, 342. 9. Kanabus-Kaminska, J., Hawari, J.A., Griller, D., and Chatgilialoglu, C., J. Am. Chem. Soc., 1987, 109, 5267. 10. Chatgilialoglu, C., Guerra, M., Guerrini, A., Seconi, G., Clark, K.B., Griller, D., Kanabus-Kaminska, J., and Martinho-Simões, J.A., J. Org. Chem., 1992, 57, 2427. 11. Clark, K.B., and Griller, D., Organometallics, 1991, 10, 746. 12. Burkey, T., Majewski, M., and Griller, D., J. Am. Chem. Soc., 1986, 108, 2218. 13. Apeloig, Y. In The Chemistry of Organosilicon Compounds, S. Patai, and Z. Rappoport (Eds), Wiley, Chichester, 1989, Chapter 2, pp. 57–225. 14. Ding, L., and Marshall, P., J. Am. Chem. Soc., 1992, 114, 5754. 15. Coolidge, M.B., and Borden, W.T., J. Am. Chem. Soc., 1988, 110, 2298. Coolidge, M.B., Hrovat, D.A., and Borden, W.T., J. Am. Chem. Soc., 1992, 114, 2354. 16. Ballestri, M., Chatgilialoglu, C., Guerra, M., Guerrini, A., Lucarini, M., and Seconi, G., J. Chem. Soc., Perkin Trans. 2, 1993, 421. 17. Cheng, Y.-H., Zhao, X., Song, K.-S., Liu, L., and Guo, Q.-X., J. Org. Chem., 2002, 67, 6638. 18. Wu, Y.-D., and Wong, C.-L., J. Org. Chem., 1995, 60, 821. 19. Liu, W.-Z., and Bordwell, F.G., J. Org. Chem., 1996, 61, 4778. 20. Borges dos Santos, R.M., and Martinho Simões, J.A., J. Phys. Chem. Ref. Data, 1998, 27, 707. 21. Borges dos Santos, R.M., Muralha, V. S. F., Correia, C.F., Guedes, R.C., Costa Cobral, B.J., and Martinho Simões, J. A., J. Phys. Chem. A, 2002, 106, 9883. 22. Sablier, M., and Fujii, T., Chem. Rev., 2002, 102, 2855. 23. Ervin, K.M., Chem. Rev., 2001, 101, 391. 24. Rienstra-Kiracofe, J.C., Tschumper, G.S., Schaefer III, H.F., Nandi, S., and Ellison, G.B., Chem. Rev., 2002, 102, 231. 25. Wetzel, D.H., Salomon, K.E., Berger, S., and Brauman, J.I., J. Am. Chem. Soc., 1989, 111, 3835. 26. Brinkman, E.A., Berger, S., and Brauman, J.I., J. Am. Chem. Soc., 1994, 116, 8304. 27. Damrauer, R., and Hankin, J.A., Chem. Rev., 1995, 95, 1137. 28. Rodriquez, C.F., and Hopkinson, A.C., Can. J. Chem., 1992, 70, 2234. 29. Modelli, A., Jones, D., Favaretto, L., and Distefano, G., Organometallics, 1996, 15, 380. 30. Shin, S.K., and Beauchamp, J.L., J. Am. Chem. Soc., 1989, 111, 900. 31. Nagano, Y., Murthy, S., and Beauchamp, J.L., J. Am. Chem. Soc., 1993, 115, 10805. 32. Dyke, J.M., Jonathan, N., Morris, A., Ridha, A., and Winter, M.J., Chem. Phys., 1983, 81, 481.
Page 1 and 2: Organosilanes in Radical Chemistry
Page 3 and 4: DEDICATION To my parents XrZstoB an
Page 5 and 6: viii Contents 3.6 Hydrogen Atom: An
Page 7 and 8: PREFACE A large number of papers de
Page 9 and 10: ACKNOWLEDGEMENTS I thank Keith U. I
Page 11 and 12: 2 Formation and Structures of Silyl
Page 19 and 20: 10 Formation and Structures of Sily
Page 27 and 28: 2 Thermochemistry 2.1 GENERAL CONSI
Page 29 and 30: Bond Dissociation Enthalpies 21 Tab
Page 31 and 32: Bond Dissociation Enthalpies 23 2.2
Page 33 and 34: Ion Thermochemistry 25 Table 2.4 Re
Page 35: Ion Thermochemistry 27 Table 2.5 El
Page 39 and 40: 32 Hydrogen Donor Abilities of Sili
Page 55 and 56: 4 Reducing Agents 4.1 GENERAL ASPEC
Page 57 and 58: General Aspects of Radical Chain Re
Page 59 and 60: Tris(trimethylsilyl)silane 53 Therm
Page 61 and 62: Tris(trimethylsilyl)silane 55 4.3.1
Page 63 and 64: Tris(trimethylsilyl)silane 57 A goo
Page 65 and 66: Tris(trimethylsilyl)silane 59 C(O)C
Page 67 and 68: Tris(trimethylsilyl)silane 61 radic
Page 69 and 70: Tris(trimethylsilyl)silane 63 86% y
Page 71 and 72: Tris(trimethylsilyl)silane 65 RO RO
Page 73 and 74: Tris(trimethylsilyl)silane 67 O AcO
Page 75 and 76: Tris(trimethylsilyl)silane 69 Tris(
Page 77 and 78: Other Silicon Hydrides 71 The reduc
Page 79 and 80: Other Silicon Hydrides 73 The decre
Page 81 and 82: Other Silicon Hydrides 75 Ph MeS O
Page 83 and 84: Other Silicon Hydrides 77 Table 4.6
Page 85 and 86: Silicon Hydride / Thiol Mixture 79
Page 87 and 88:
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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164 Consecutive Radical Reactions A
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168 Consecutive Radical Reactions r
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170 Consecutive Radical Reactions E
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174 Consecutive Radical Reactions A
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176 Consecutive Radical Reactions P
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178 Consecutive Radical Reactions f
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182 Consecutive Radical Reactions 1
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184 Consecutive Radical Reactions 8
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186 Silyl Radicals in Polymers and
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Page 225 and 226:
220 List of Abbreviations PED photo
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222 Index Carbonyl sulfide 111 Carb
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224 Index Organosilicon boranes 2,
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226 Index Triethylsilane as mediato
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