The role of the M−PR2 fragment in hydrophosphination: from mechanisms to catalysis

• Main Author: Belli, Roman
• Other Authors: Rosenberg, Lisa
• Format: Others
• Language: English; en
• Published: 2019
• Subjects: Hydrophosphination; Hydrosilylation; Low valent phosphorus ligands; Mechanisms; Metal Catalysis
• Online Access: http://hdl.handle.net/1828/11037

In this thesis, the synthesis and reactivity of metal complexes containing phosphido (PR2−) and phosphenium (PR2+) ligands for the hydrophosphination of alkenes were investigated. The mechanisms of hydrophosphination mediated by these M-PR2 fragments were explored. Based on previous work in the Rosenberg group, Ru(η5-indenyl) complexes were explored and developed as catalysts for hydrophosphination. It was determined that Ru-phosphido complexes are key intermediates in the hydrophosphination of electron-deficient alkenes. A detailed study on the mechanisms of hydrophosphination catalyzed by the phosphido complexes Ru(η5-indenyl)(PPh2)(L)(PPh3) (4a, L = NCPh; b, L = PPh2H; c, L = CO) was performed. Evidence for product inhibition was found for this catalyst system using Reaction Progress Kinetic Analysis. Product inhibition is consistent with the observed catalyst resting state of a complex containing product phosphines and the determination that substitution of the product phosphine from Ru is rate-limiting. The ancillary ligands (L) of 4 were found to influence catalytic activity by enabling catalyst deactivation (L = NCPh) or off-cycle processes including alkene telomerization (L = CO). Proposed mechanisms for catalysis were devised based on these findings. These results are important mechanistic insights that will be useful for designing new catalysts for hydrophosphination. The unprecedented viability of metal phosphenium complexes as intermediates in hydrophosphination was also explored. Three Mo phosphenium complexes were synthesized via P-H bond hydride abstraction from coordinated secondary phosphines, PR2H. These complexes were found to mediate the stoichiometric hydrophosphination of alkenes and ketones. In particular, trans-[Mo(CO)3(PPh2H)2(PPh2)]+ (13) mediates the hydrophosphination of a wide scope of alkenes that includes ethylene, propene and 1-hexene, which are challenging substrates for metal-catalyzed hydrophosphination. Preliminary attempts were conducted to render this synthetic phosphenium-mediated hydrophosphination catalytic. These results provide evidence for the putative steps of a hydrophosphination cycle utilizing metal phosphenium complexes as intermediates. The phosphenium complexes trans-[Mo(CO)4(PR2H)(PR2)] (12a R = Tolp2, b R = Ph) were also investigated as Lewis acid catalysts for hydrosilylation. A tentatively-assigned η1-HSiEt3 adduct of 12a, [Mo(CO)4(PTolp2H)(PTolp2{HSiEt3})] (20a), was observed by low temperature 31P{1H} NMR and was studied computationally. Complex 12b is proposed to behave as a Lewis acid catalyst for hydrosilylation. An off-cycle equilibrium is proposed that results in the formation of EtSi+. This work is a unique example of P(III) Lewis acid catalysis, of which there are few examples in the literature. === Graduate === 2020-07-29