Synthesis and Reactivity of Organometallic and Coordination Complexes of Mg and Ni

by Louise M Guard

Institution: Yale University
Year: 2015
Keywords: Chemistry
Posted: 02/05/2017
Record ID: 2120502
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The first three chapters of this thesis summarize the synthesis and reactivity of a series of Mg complexes supported by both meridinally and facially binding neutral nitrogen based ligands. Chapter 1 is a review of Grignard reagents and covers both the history and preparation of these compounds, as well as their speciation in the solid state and in solution. Additionally, contemporary chemical applications of Grignard reagents are also discussed. Chapter 2 recounts the synthesis and characterization of a series of 2,2':6',2'-Terpyridine (terpy) Mg complexes. The selective reaction of terpy with MgX2 over RMgX and R2Mg is rationalized computationally. Chapter 3 details the preparation of Mg complexes supported by Tris(2-dimethylaminoethyl)amine (Me6tren). The reactivity of organometallic complex (Me6tren)MgMe2 is further investigated with a variety of small molecules. Chapter 4 begins with a short review of Ni catalyzed Suzuki-Miyaura reactions and continues with the synthesis of a series of 1,1'-Bis(diphenylphosphino)ferrocene (dppf) supported Ni(0), (I) and (II) complexes. The catalytic activity of the compounds was tested and all precatalysts were found to be active at room temperature. The speciation of Ni during catalysis was investigated using both EPR and NMR spectroscopies and found to be predominantly Ni(I). Pathways to form Ni(I) from even electron Ni species were elucidated and found to involve comproportionation, which was also investigated computationally.