An x-ray electron spectroscopic study of ?-allyl complexes of palladium

XPS Investigations of (1,4,7-trimethyl-1,4,7-triazacyclononane)RhMe3and [1,1,1-tris((dimethylphosphino)methyl)ethane]RhMe3and Their Rh−C Cleavage Derivatives. Comparison of Hard- and Soft-Ligated Rhodium Organometallics

“…0.1−0.26, depending on the scale 12 ) suggests the chloride complexes should have slightly higher BEs than the bromide analogues, consistent with the best-line interpretations of Figure . This was shown to be the case in a series of dihalotitanocene derivatives, where the chloride complexes were 0.1−0.3 eV higher in BE than the corresponding bromides. 6c, However, there are also a few reports where the trend goes in the other direction. , Clearly, σ-inductive effects and π-donor effects of the halide ligands, and the response of the ancillary ligands in the complex to the exchange of a halide for a methyl group, all combine in a way that is characteristic of a given system and is not identical for all metals. In addition, relaxation effects during photoionization may be different for different metal systems, so that the relative response of initial states and final states to ligand changes could also be different.…”