Browsing by Author "Rehbein, Steven Mark"

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Catalysis with early and late transition metals: C-H activation at tantalocene hydrides and oxidative addition at palladium solvato complexes
(Montana State University - Bozeman, College of Letters & Science, 2021) Rehbein, Steven Mark; Chairperson, Graduate Committee: Sharon Neufeldt; Matthew J. Kania and Sharon R. Neufeldt were co-authors of the article, 'Experimental and computational evaluation of tantalocene hydrides for C-H activation of arenes' in the journal 'Organometallics' which is contained within this dissertation.; Steven M. Rehbein and Sharon R. Neufeldt were co-authors of the article, 'Solvent coordination to palladium can invert the selectivity of oxidative addition' in the journal 'Organometallics' which is contained within this dissertation.
Herein we present our work on transition metal catalysis using metals from two sides of the periodic table: C-H activation catalyzed by early transition metals and cross-couplings catalyzed by late transition metals. In the first part, a synergistic experimental and computational approach was employed to investigate the possibility of extending the reactivity of bent tantalocene hydrides beyond aromatic C-H activation to enable activation of aliphatic substrates. In situ monitoring of the characteristic 1 H NMR metal hydride signals in the reaction of Cp 2TaH 3 and related complexes with deuterated aromatic substrates allowed for the evaluation of reaction kinetics of catalyst decomposition, H/D exchange, and off-cycle reactions. The insight gained from in situ reaction monitoring with aromatic substrates, combined with computational analyses, allowed for the extension of this chemistry to intra- and intermolecular aliphatic C-H activation. This work represents the first example of aliphatic C-H activation by homogeneous tantalum hydrides. In the second part, we provide compelling evidence that solvent coordination to palladium during oxidative addition of chloroaryl triflates can result in an inversion of chemoselectivity of this step. Previous investigations attributed a solvent-dependent switch in chemoselectivity to the propensity of polar solvents to stabilize anionic transition states of the type [Pd(P t Bu 3)(X)]- (X = anionic ligand). However, our detailed investigations show that solvent polarity alone is not a sufficient predictor of selectivity. Instead, solvent coordinating ability is selectivity-determining, with polar coordinating and polar noncoordinating solvents giving differing selectivity, even in the absence of anionic ligands 'X'. A solvent-coordinated bisligated transition state of the type Pd(P t Bu 3)(solvent) is implicated by density functional theory calculations. This work provides a new mechanistic framework for selectivity control during oxidative addition.