Online

Cibuzar, Michael Patrick

Chemistry

2019

Ph. D.

Investigation of catalytic main-group bond forming reactions is the basis of this dissertation. Coupling of group 14 and 15 elements by several different methods has been achieved. The influence of Si--N heterodehydrocoupling on the promotion of [alpha]-silylene elimination was realized. Efficient Si--N heterodehydrocoupling by a simple, earth abundant lanthanide catalyst was demonstrated. Significant advances in hydrophosphination by commercially available catalysts was achieved by photo-activation of a precious metal catalyst. Exploration of (N3N)ZrNMe2 (N3N = N(CH2CH2NSiMe3)33--) as a catalyst for the cross-dehydrocoupling or heterodehydrocoupling of silanes and amines suggested silylene reactivity. Further studies of the catalysis and stoichiometric modeling reactions hint at [alpha]-silylene elimination as the pivotal mechanistic step, which expands the 3p elements known to engage in this catalysis and provides a new strategy for the catalytic generation of low-valent fragments. In addition, silane dehydrocoupling by group 1 and 2 metal bis(trimethylsilyl)amide complexes was investigated. Catalytic silane redistribution was observed, which was previously unknown for d0 metal catalysts. La[N(SiMe3)2]3THF2 is an effective pre-catalyst for the heterodehydrocoupling of silanes and amines. Coupling of primary and secondary amines with aryl silanes was achieved with a loading of 0.8 mol % of La[N(SiMe3)2]3THF2. With primary amines, generation of tertiary and sometimes quaternary silamines was facile, often requiring only a few hours to reach completion, including new silamines Ph3Si(nPrNH) and Ph3Si(iPrNH). Secondary amines were also available for heterodehydrocoupling, though they generally required longer reaction times and, in some instances, higher reaction temperatures. By utilizing a diamine, dehydropolymerization was achieved. The resulting polymer was studied by MS and TGA. This work expands upon the utility of f-block complexes in heterodehydrocoupling catalysis. Stoichiometric and catalytic P--E bond forming reactions were explored with ruthenium complexes.Hydrophosphination of primary phosphines and activated alkenes was achieved with 0.1 mol % bis(cyclopentadienylruthenium dicarbonyl) dimer, [CpRu(CO)2]2. Photo-activation of [CpRu(CO)2]2 was achieved with a commercially available UV-A 9W lamp. Preliminary results indicate that secondary phosphines as well as internal alkynes may be viable substrates with this catalyst. Attempts to synthesize ruthenium phosphinidene complexes for stoichiometric P--E formation have been met with synthetic challenges. Ongoing efforts to synthesize a ruthenium phosphinidene are discussed. The work in this dissertation has expanded the utility of metal-catalyzed main-group bond forming reactions. A potential avenue for catalytic generation low-valent silicon fragments has been discovered. Rapid Si--N heterodehydrocoupling by an easily obtained catalyst has been demonstrated. Hydrophosphination with primary phosphines has been achieved with a commercially available photocatalyst catalyst, requiring only low intensity UV light.