wald and E. K. Ralph, Accounts Chem. Res., 4, 107 (1971). ( 20) Note Added in Proof. Since the submission of our manuscript Grunwald and Fong's full report has appeared (E. Grunwald and D. W. Fong, J. Amer. Chem. Soc., 94, 7371 (1972)). The activation parameters of the rate constant, which they assign as ku, are AH* = 0.7 kcal mol-1 and 5* = -18 eu. The large differences between these values and those found by us for the ruthenium system seem to support our conclusion that kG (eq 14) is the ratelimiting step in the proton exchange reaction of Ru(NH3)5NH22 + .
X-Ray photoelectron spectroscopy was used to determine chemical shifts in the binding energies of electrons in the "3p" and ''3d" orbitals of 32 arsenic compounds. The resulting binding-energy shifts are discussed in terms of the influence of atoms directly bonded to the arsenic. The usual trend of an increase in binding energy with increasing substituent electronegativity was observed. Analogous nitrogen, phosphorus, and arsenic chemical environments were compared both experimentally and theoretically, with the aid of atomic SCF calculations, to determine the relative chemical shifts. Some data are also presented on the effects of using different referencing compounds.
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