13C Hyperfine Splittings in the Electron Spin Resonance Spectra of HCO and FCO
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7.This process is just the reverse of the usual process of spin polarization of a pair of electrons in a σ bond by an unpaired π electron. This effect has been observed and discussed previously for by D. W. Ovenall and D. H. Whiffen, Mol. Phys. 4, 135 (1961).
8.G. Herzberg and D. A. Ramsay, Proc. Roy. Soc. (London) A233, 34 (1955).
9.This assumption is based on the fact that the primary factor governing the transfer of spin density from the carbon atom to the oxygen atom is the carbon‐oxygen exchange integrals. The nature of the other atom bonded to the carbon affects these integrals only indirectly through the change in bond angle and the relative amounts of s and p character in plus the change in spin density on the carbon atom. Rough estimates of these two effects show that they are not very large and that they tend to cancel each other. The increased character of in going from HCO to FCO tends to reduce the amount of spin density on the oxygen (cf. A. D. Walsh, J. Chem. Soc. 1953, 2266). On the other hand, the unpaired electron density on the F atom in FCO is less than it is on the H atom in HCO, and this increases the spin density available to the carbon and oxygen atoms.
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