The proton affinities of phenyl phosphine and cyclohexylphosphine were measured by determining the equilibrium constants of proton transfer equilibria with a pulsed electron beam high ion source pressure mass spectrometer. These proton affinities combined with values for methyl and phenyl phosphines and the analogous amines provide an interesting comparison of the methyl and phenyl substituent effects on the basicities of phosphine and ammonia. Methyl substitution increases the basicity of both ammonia and phosphine; however, the increase is significantly larger for the phosphine. Phenyl substitution increases the basicity of ammonia and phosphine and the increase for phosphine is very much larger. Calculations at the STO-3G, 4-31G, STO-3G*, and 4-31G* (* with d orbitals) for PH3, MePH2, PhPH2, the protonated species, and the nitrogen analogues predict proton transfer reaction energies in good agreement with the experimental results. A shortening of the C—P bond is predicted for protonation of MePH2 and particularly PhPH2, while a lengthening of the C—N bond is predicted for the corresponding nitrogen compounds. The much stronger increase in proton affinity of the phosphines caused by phenyl substitution is due to the stabilization of the phenyl phosphonium ion by π donation from the phenyl group to the empty orbitals of phosphorus in the [Formula: see text] group; in contrast, in the amines, it is the free base aniline which is stabilized by conjugation of the nitrogen lone pair with the aromatic ring. This stabilization of the free base is less important in phenyl phosphine. The participating empty orbitals of phosphorus in the conjugation of phenyl with [Formula: see text] in phenyl phosphonium are mostly π* with some -πd participation. The stabilization of the aniline free base contributes considerably more than the conjugation in the phosphonium ion, to the phenyl substituent difference for the amines and phosphines. The factors involved in the bigger substituent effect of methyl in the phosphines are somewhat similar to those for phenyl: stabilization of the methyl amine by conjugation of the nitrogen lone pair with empty orbitals of CH3 and stabilization of the [Formula: see text] by hyperconjugation. An alternate description can be given in terms of hybridization changes.
A Combined Experimental and Computational Study of Halogen and Hydrogen Bonding in Molecular Salts of 5-Bromocytosine