6851
Remote Inductive Effects Evaluated by X-Ray Photoelectron Spectroscopy (ESCA) James C. Carver, Robert C. Gray, and David M. Hercules*’ Contribution from the Department of Chemistry, University of Georgia, Athens, Georgia 30602. Received April 3, 1974
Abstract: Core-electron binding energies of terr-butyl alcohol and three of its fluoro derivatives were measured by ESCA to evaluate remote inductive effects. Various charge calculations are analyzed as to their effectiveness in predicting shifts in electron binding energies caused by inductive effects. The empirical methods of Jolly and Pauling are used as well as the semiempirical CNDO, INDO, and extended Hiickel methods. In addition a new empirical method is introduced based on a modification of Sanderson’s electronegativity calculations. It was determined that chemical shifts caused by remote atoms are often sufficient to help in molecular identification. If shift tables were to be formulated, similar to those used in nmr, the usefulness of ESCA in qualitative analysis would be enhanced. Accurate predictions of binding energy shifts are found when using CNDO, INDO, and modified Sanderson charge calculations.
The
study of charge distribution in molecules has been one of the most frequent applications of electron spectroscopy ( E S C A ) to chemistry. To enhance the understanding of chemical shift data, it has been c o m mon to compare experimentally measured core-electron binding energies with various charge calculations, including ab initio2 and semiempirical 3, MO calculations along with several empirical methods based on electr0negativity.j Few studies, however, have sought to estimate the effect of remote atoms on the binding energies of core electrons.6 We have chosen a simple, but revealing, system to evaluate remote inductive contributions to ESCA chemical shifts. The series includes tert-butyl alcohol, trifluoro-tert-butyl alcohol, hexafluoro-tert-butyl alcohol, a n d perfluoro-tert-butyl alcohoL7 The lack of 7~ bonding and the large inductive effects of fluorine make this system particularly attractive. Charge calculations were d o n e using CNDO, INDO, extended Hiickel (EH), Jolly’s m e t h ~ d , ~and ” a modified Sanderson (MS) approach developed in this laboratory.* Molecular potential calculations were included where appropriate.
Experimental Section ESCA spectra were obtained using an AEI-ES100 electron spectrometer having an aluminum anode (hv = 1486.6 eV). Since the (1) John Simon Guggenheim Memorial Fellow, 1973-1974. (2) D. T. Clark and D. B. Adams, J . Chem. SOC., Faraday Trans. 2, 68,1819 (1972); J. Electron Spectrosc. Relat. Phenomena, 1,302 (1973). (3) M. E. Schwartz, J. Amer. Chem. SOC., 94,6899 (1972). (4) M. E. Schwartz, J. Amer. Chem. SOC.,94,6298 (1972). ( 5 ) (a) W. L. Jolly and W. B. Perry, J. Amer. Chem. SOC., 95, 5442 (1973); (b) K. Siegbahn, C. Nordling, A. Fahlman, R. Nordberg, I
