Abstract: | Proton affinities of a series of triphenyl Group Va compounds have been determined by bracketing using reactant ion monitoring: (C6H5)3N = 904 ± 8 kJ mol?1, (C6H5)3P = 968 ± 5 kJ mol?1, (C6H5)3As = 904 ± 8 kJ mol?1 and (C6H5)3Sb = 846 ± 8 kJ mol?1. The large difference in substituent effect of phenyl for hydrogen between As or P and N may result from overlap of the 2p orbitals of N with the sp2 orbitals on the ring carbons and lack of overlap for P or As. Proton affinities of phenylalkylphosphine oxides are essentially the same, 904 ± 8 kJ mol?1, independent of alkyl group. |