ELECTRONIC FACTORS OF CARBON - HYDROGEN AND DOUBLE-BONDED CARBON BOND ACTIVATION: EXPERIMENTAL INFORMATION FROM ULTRAVIOLET AND X-RAY PHOTOELECTRON SPECTROSCOPIES (CORE, VALENCE, OLEFIN).

摘要

Principles of transition metal electronic structure are presented to enable an understanding of the activation of C-H and C=C bonds by metals. A multitechnique approach utilizing core and valence photoelectron spectroscopies (p.e.s.) and molecular orbital calculations has been used to gain these insights. In the first half of the dissertation three principles are developed: ligand additivity, core-valence ionization correlation, and ring methylation. In the latter half of the dissertation these principles are seen to be crucial for understanding ionization data for the C-H and C=C activated species. Additive (with respect to ligand substitution) electronic effects, including additive core and valence ionization potentials, are shown in the p.e.s. of phosphine substituted molybdenum carbonyls. These additive effects demonstrate that the electronic effects of ligand substitution are predictable from empirical models. The core-valence ionization correlation enables direct comparison of XPS (core) and UPS (valence) ionization data and allows separation of bonding and overlap induced valence shift effects from Coulombic and relaxation shift effects. In the study of trimethylphosphine substituted cyclopentadienylmanganese tricarbonyl complexes, both the ligand additivity and core-valence ionization correlation principles are less valid than for the molybdenum carbonyl complexes because of loss of the very influential carbonyl backbonding. Methylation of the cyclopentadienyl ring in this system adds another independent variable of electronic structure perturbation and enables separation of the one-center and two-center Coulombic contributions to the core shifts. The above principles are used in the later chapters to show that the initial activation of the C-H bond in alkenylmanganese tricarbonyl complexes is dominated by the interaction of the C-H sigma bonding level with empty metal acceptor levels. The activation stops at the agostic stage rather than proceeding to full β-hydribe abstraction because there is, in these molecules, no gain in the number of pi electrons between the allyl and diene hydride endpoints of the abstraction cycle. Activation of the C=C bond in the cyclopentadienylmetal olefins is similar for Co and Rh complexes despite little similarity in the valence ionization spectra. The spectral differences are largely caused by the relaxation energy differences between Co and Rh. These complexes also provide interesting examples of electron delocalization through the metal. Permethylation of the cyclopentadienyl ring shifts the olefin pi ligand ionizations more than the expected Coulombic shift.