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An Adventure in Space (Group) and (Reaction) Time: Divergent Synthesis of Heterobimetallic Complexes of Zinc with Lewis Acids
Kelsey, Shaun R.
Kelsey, Shaun R.
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Abstract
Assembly of heterobimetallic complexes is challenging due to the propensity of ditopic ligands to bind metals unselectively. This challenge is exacerbated in situations in which two redox-inactive metals are to be coordinated within one ligand framework, as such metals can bind in a variety of coordination environments. In this thesis, the preparation and isolation of four heterobimetallic complexes of zinc, a redox-inactive first-row transition metal, with a range of other redox-inactive Lewis acidic metals (Na+, Ca2+, Nd3+, and Y3+) are reported. The complexes were prepared via a divergent route in which a common monometallic zinc complex featuring a crown-ether-like site within a macrocyclic structure was selectively metallated with triflate salts of sodium, calcium, neodymium, and yttrium. One-dimensional 1H and two-dimensional 1H–1H Correlation Spectroscopy (COSY) Nuclear Magnetic Resonance (NMR) studies provide robust support for synthesis of the target heterobimetallic compounds. Single crystals suitable for X-ray diffraction analysis were grown of the [Zn,Nd] complex, revealing the expected atomic connectivity within the macrocyclic framework. In the solid state, the zinc center is five-coordinate, with a terminal acetonitrile ligand; this finding contrasts with the structure of the analogous [Ni,Nd] complex that instead features a four-coordinate nickel center. These results are discussed in the context of developing model compounds for study of the spectroscopic and electrochemical properties of heterobimetallic complexes containing redox-inactive Lewis acids.
Description
This undergraduate thesis was submitted In partial fulfillment of the requirements for the degree of Bachelor of Science with Honors in Chemistry.
Date
2019-05
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Department of Chemistry, University of Kansas