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By C.H. Bamford and C.F.H. Tipper (Eds.)

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Additional info for Decomposition of Inorganic and Organometallic Compounds: Homogeneous Decompostion of Hydrides, Decompostion of Inorganic Oxides and Sulphides; Halides and Derivatives; Metal Alkyls, Aryls, Carbonyls and Nitrosyls

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The height of the barrier, V, a x , is a few kcal . mole-' at most. If it is assumed for simplicity that V m a X= 0, it follows that p' =p2 = 1. In all cases with p , = p 2 = 1(also if V, # V,), V is linearly dependent on n. V as a function of n has a maximum only if either p1 or p 2 ,or both, are larger than 1. Since ni < 1, the decrease of energy with partial formation of one of the bonds, Vinfi, is smaller than the amount proportional to the fractional bond order (Vini) if pi > 1. The larger pi the smaller is the energy set free in the fractional bond forming process.

2, pp. 346-351). The rates of slow proton transfer reactions may be correlated with the differences of pK values of donor and acceptor. On the other hand, the pK difference cannot be the only important quantity. Therefore, a need exists for a better qualitative or semi-quantitative understanding of the factors which govern the height of the energy barrier to proton transfer. Furthermore, some knowledge of the approximate position of the proton on the reaction coordinate in the transition state as well as of the curvature of the barrier is needed for a calculation of the primary isotope effect in proton transfer reactions [93-96,1301.

134. Goodall [134] plotted log ( k H l k D for ) twenty different reactions of this type against the difference of pK values of donor and acceptor. They found that the isotope effect goes through a maximum near ApK = 0. A similar observation has been made by Longridge and Long [135] for the hydrogen isotope effect in proton transfer reactions from protonated aromatic compounds t o H 2 0 and other oxygen bases. Furthermore, Kresge et al. [136] have observed a maximum in a plot of k H / h , , versus log k H for the hydrolyses of various vinyl ethers.

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