Chemical Bonding and Geometry of Molecules by Ryschkewitsch G.E.

By Ryschkewitsch G.E.

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21. P. R. Tremaine, E. E. Isaacs, and J. A. Boon, Hydrothermal chemistry applied to in situ bitumen recovery. Chem. Can. April, 29-33 (1983). 22. V. Tunnicliffe, Hydrothermal vent communities of the deep sea. Am. Sci. 80, 336-349 (1992). 23. R. M. Kelly, J. A. Baross and M. W. W. Adams, Life in boiling water. Chem. Br. 30, 555-558 (1994); M. W. W. Adams and R. M. Kelly, Enzymes from microorganisms in extreme environments. Chem. Eng. News December 18, 32-41 (1995). 24. R. M. Izatt, S. E. Gillespie, X.

31 In 1989, Allen 32 presented a fresh approach in which he redefined electronegativity as the average one-electron energy of the valence shell electrons in the free atoms. He suggested that the electronegativities of the elements so calculated are sufficiently important that they should be included graphically in the periodic table as a third dimension. Parr, Pearson, and others have considered calculated electron densities in molecules as the basis for electronegativity scales. 48) where E is the electronic energy, N is the number of electrons, and v is the external potential (due mainly to the atomic nuclei) acting on the electrons.

Whereas triphenylmethane (R = C6H5) is unreactive toward water, triphenylsilane hydrolyzes (reacts with water) to give triphenylsilanol [(C6Hs)3Si--OH] and hydrogen gas (cf. H - + H20 ~ O H - + He): (C6H5)38i ~+- - - H ~HO > (C6H5)3SiOH + H2 ~- _ + - H~+ Similarly, it comes as no surprise to learn that Si--C1 bonds are much more susceptible to hydrolysis than C--C1 bonds, since Si--C1 has the greater electronegativity difference. These naive predictions can be misleading, however. The R 3 C - - F bond should be very polar, and hydrolysis might be expected to give R 3 C - - O H and HF.

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