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166 Tomioka, H; Hirai, K; Tabayashi, K; Murata, S; Izawa, Y; Inagaki, S; Okajima, T, J Am Chem Soc, 1990, 112, 7692 167 Gosavi, R K; Torres, M; Strausz, O P, Can J Chem, 1991, 69, 1630 168 For a review, see Gaspar, P P; West, R, in The Chemistry of Organic Silicon Compounds, 2nd ed, Rappoport, Z; Apeloig, Y, Eds, Wiley, New York, 1999, Part 3, pp 2463 2568 169 Kira, M; Ishida, S; Iwamoto, T; Kabuto, C, J Am Chem Soc, 1999, 121, 9722 9723, and references therein 170 (a) Suchard, S N, Selected Spectroscopic Constants for Selected Heteronuclear Diatomic Molecules, Air Force Report No SANSO-TR-74-82, U S Government Printing O ce, Washington, DC, 1974 (b) Gilles, A; Masanet, J; Vermeil, C.





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, Chem Phys Lett, 1974, 25, 346 171 Davis, J H; Goddard III, W A, J Am Chem Soc, 1977, 99, 7111 7121 172 Back, T G; Kerr, R G, Can J Chem, 1982, 60, 2711, and references therein 173 Rauk, A; Alewood, P F, Can J Chem, 1977, 55, 1498, and references therein 174 Hrovat, D A; Waali, E E; Borden, W T, J Am Chem Soc, 1992, 114, 8698 8699 175 Kim, S-J; Hamilton, T P; Schaefer III, H F, J Am Chem Soc, 1992, 114, 5349 5355 176 Travers, M J; Cowles, D C; Cli ord, E P; Ellison, G B, J Am Chem Soc, 1992, 114, 8699 8701 177 For a review of nitrenium ions, see Scott, A P, Ph D.

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Figure 6.14. The nuclear overhauser effect (NOE). Two protons (i and j) may each exist in a low-energy state ( ) or a high-energy state ( ) in a magnetic eld (B0 ) as previously described (Figure 6.11). Transitions between these states at equilibrium (arrows) occur by cross-relaxation with rate constants which are equal in opposite directions (for clarity, only k1 and k 1 between and are shown). However, when this situation is perturbed by exposure to radiofrequency radiation, the equilibrium is disturbed (k1 = k 1 ). A change in magnetization of i changes the magnetization of j for a time period after the perturbation. This is the nuclear overhauser effect (NOE) and the rate of build-up of this is equal to the crossrelaxation rate.

Dissertation, The University of New England, Armidale, N S W, Australia, 1991 178 Gibson, S T; Greene, J P; Berkowitz, J, J Chem Phys, 1985, 83, 4319 179 Ford, G P; Herman, P S, J Am Chem Soc, 1989, 111, 3987 180 (a) Multiple Bonds and Low Coordination in Phosphorus Chemistry, Regitz, M; Scherer, O J, Eds, Georg Thieme Verlag, Stuttgart, 1990 (b) Cowley, A H; Kemp, R A, Chem Rev, 1985, 85, 367 181 Burford, N; Parks, T M; Royan, B W; Borecka, B; Cameron, T S; Richardson, J F; Gabe, E J; Hynes, R, J Am Chem Soc, 1992, 114, 8147 8153 182 Ford, G P; Scribner, J D, J Am Chem Soc, 1981, 103, 4281 183 (a) Li, Y.

; Abramovitch, R A; Houk, K N, J Org Chem, 1989, 54, 2911 (b) Ohwada, T; Shudo, K, J Am Chem Soc, 1989, 111, 34 184 Worthington, S E; Cramer, C J; Dulles, F J; Storer, J W, http://polluxchemumn/STgaps/ 185 Elevation of the HOMO, nO , of the carbonyl group above j j is expected on the basis of the orbital interactions, and the SHMO energy of the 2p orbital of a monocoordinated oxygen atom (Table 51, 5) This is consistent with increased basicity of the carbonyl oxygen relative to the p bond of ethylene but is not consistent with the observed ionization potentials (IPs) of carbonyls and structurally related alkenes For instance, the IP of formaldehyde is 1088 eV and that of ethylene is 1051 eV.

7.1 10 3 rad/h or 7.1 mrad/h (c) The absorbed dose rates from proton recoils and gamma rays are then added together to yield the absorbed dose rate in rad/h, or

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