Electronic Thesis and Dissertation Repository

Degree

Master of Science

Program

Chemistry

Supervisor

Dr. John Corrigan

2nd Supervisor

Dr. Mark Workentin

Joint Supervisor

Abstract

Research on phosphine and N-heterocyclic carbene (NHC) terminated coinage metal complexes of the type L-M-X (L = NHC, Phosphine and X = S, Se) has been well-documented, however, the synthesis of coinage metal complexes of the type containing functional chalcogenolate ligands remains largely unexplored. Previous studies on sulfur containing precursors have provided an effective pathway for their incorporation onto coinage metal complexes through the generation of trimethylsilylsulfides and thiolates.

The reaction of NHC-coinage metal salts, [(NHC)MX] (X = halide, carboxylate, etc.), with an azide-modified ligand affords clickable NHC-coinage metal thiolates: [(iPr2-bimy)Au-1-SCH2-2,5-(CH3)2Ph-4-CH2N3] (1), [(IPr)Au-1-SCH2-2,5-(CH3)2Ph-4-CH2N3] (2), [(IPr)Ag-1-SCH2-2,5-(CH3)2Ph-4-CH2N3] (3) and [(IPr)Cu-1-SCH2-2,5-(CH3)2Ph-4-CH2N3] (4) (R = {CH2Ph(CH3)2CH2N3}, iPr2-bimy =1,3-di-isopropylbenzimidazol-2-ylidene, IPr = 1,3-bis(2,6-di-iso-propylphenyl)imidazol-2-ylidene). Single crystal X-ray analysis of 1-4 show that they are two-coordinate, nearly linear, with a terminally bound thiolate ligand. The successful conversion of [(NHC)MX] from X = halide, carboxylate, etc. to X = SR is further confirmed by heteronuclear spectroscopy, and elemental analysis. The complexes are also found to be luminescent at 298 K. The results of the UV-Vis and photoluminescence spectroscopy are also presented.

The Strain Promoted Alkyne-Azide Cycloaddition (SPAAC) reaction of one of the complexes with bicyclononynylmethanol (BCN-OH), a cyclooctyne, has also been demonstrated in order to illustrate the reactivity of the azide moiety toward strained-alkynes (5). Additionally, the reaction kinetics have also been determined, further confirming that the azide moiety is available for SPAAC reaction. Altogether, a novel approach towards functional coinage-metal thiolate complexes is presented for post-assembly modifications through SPAAC chemistry.

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