Synthesis, Structure, and C-H Activation Reactivity of the Unsolvated Samarium Methyl Complex, [(C5Me5)2SmMe]3, Obtained From the Samarium Cation, [(C5Me5)2Sm][BPh4]
226th National Meeting of the American Chemical Society: Lanthanides and Actinides / New York, New York
The unsolvated cations [(C5Me5)2Ln][µ-Ph2BPh2] have proven to be good precursors for the difficult synthesis of the sterically crowded (C5Me5)3Ln complexes. The(C5Me5)3Ln complexes must be made in the absence of THF, which they ring open, and they must be prepared in an environment in which no other sterically more acceptable products can form. The precipitation of KBPh4 from the reaction of [(C5Me5)2Ln][µ-Ph2BPh2]and KC5Me5 in arenes meets these requirements. The [(C5Me5)2Ln][µ-Ph2BPh2]complexes also have the potential to be precursors to other (C5Me5)2LnR which cannot be accessed THF-free in any other way. In this contribution, the reaction of [(C5Me5)2Ln][µ-Ph2BPh2] with LiMe is described. This provides the first structural data on an unsolvated samarocene methyl complex as well as the opportunity to study its C-H activation reactivity in the absence of coordinating solvents. The unusual structure of [(C5Me5)2SmMe]3, which includes both terminal and bridging methyl groups, will be described as well as its reaction chemistry in toluene, which includes new metalated arene products and their CO2 derivatives such as the meta-tolyl-carboxylate complex,[(C5Me5)2Sm(µ-h2-4-O2CC7H7)]2.
Evans, William J.; Perotti, Jeremy M.; and Ziller, Joseph W., "Synthesis, Structure, and C-H Activation Reactivity of the Unsolvated Samarium Methyl Complex, [(C5Me5)2SmMe]3, Obtained From the Samarium Cation, [(C5Me5)2Sm][BPh4]" (2003). Chemistry and Physics Faculty Proceedings, Presentations, Speeches, Lectures. 3.