Towards terminal rare earth imido complexes

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Knott, Jackson P.
University of Lethbridge. Faculty of Arts and Science
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Lethbridge, Alta. : University of Lethbridge, Dept. of Chemistry & Biochemistry
The development of rare earth complexes supported by a bisphosphinimine pyrrole-based pincer ligands is described herein. Synthesis of these species was conducted via alkane elimination and salt metathesis pathways. These complexes and their precursors were prepared and characterized by multi-dimensional (1-, pseudo-2-, and 2-dimensional), multi-nuclear (1H, 2H, 11B, 13C, 19F, and 31P) NMR spectroscopy, single-crystal X-ray diffraction analysis and elemental analysis. Systematic modifications to the ancillary ligand and the resulting impact on complex reactivity is also presented with the ultimate goal of generating a species that bears a rare earth-nitrogen double bond. Specifically, electron withdrawing (Ph) and donating (iPr) groups were installed on the phosphinimine P atoms of the ligand and Pipp (4-iPrC6H4) and Pm (4,6-dimethylpyrimidine) were utilized on the phosphinimine nitrogen atoms. Each iteration of the ancillary ligand led to distinct and unique reactivities upon complexation to a rare earth metal.
Diphosphonates , Organotransition metal compounds , Rare earth metal compounds , Rare earth metals