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Synthesis and Characterization of (Phospine)- and (N-Heterocyclic Carbene)Gold(I) Halides, Azides, Alkynyls, Triazoles, and Dendrimers and the Synthesis and Characterization of Gold(I) Thiacrown Macrocycles

Robilotto, Thomas J.

Abstract Details

2011, Doctor of Philosophy, Case Western Reserve University, Chemistry.

New (phosphine)- and (N-heterocyclic carbene)gold(I) halides and azides have been synthesized and characterized as starting materials for the synthesis of gold(I) alkynyls and triazoles. For the synthesis of the gold(I) alkynyls, a one-pot synthesis of a gold(I) halide and terminal alkyne in the presence of a base forms a gold(I) alkynyl that will precipitate out of solution. For the synthesis of the gold(I) triazoles, a gold(I) azide and a terminal alkyne form a [3+2] cycloaddition adduct having a gold-carbon bond. The triazolate complex precipitates out of solution. The methods has been extended to alkyne-functionalized poly(benzyl ether) dendrimers. All of these gold(I) materials have been synthesized as part of a broad research endeavor in medicinal gold chemistry.

Three gold(I) thiacrown ether macrocycles have been synthesized. The simplest gold(I) thiacrown ether, [Au([18]aneS6)][SbF6], has been crystallographically characterized, the structure shows that the gold(I) moiety is bound to four sulfur atoms. The synthesis for the other gold(I) monoaza-pentathia macrocycles involves a more complex procedure, with the final step being the gold(I) addition. The objective is gold(I) insertion opposite abasic lesions in duplex DNA.

Thomas Gray (Advisor)
Irene Lee (Committee Chair)
Burda Clemens (Committee Member)
James Burgess (Committee Member)
Horst von Recum (Committee Member)
314 p.

Recommended Citations

Citations

  • Robilotto, T. J. (2011). Synthesis and Characterization of (Phospine)- and (N-Heterocyclic Carbene)Gold(I) Halides, Azides, Alkynyls, Triazoles, and Dendrimers and the Synthesis and Characterization of Gold(I) Thiacrown Macrocycles [Doctoral dissertation, Case Western Reserve University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=case1282230551

    APA Style (7th edition)

  • Robilotto, Thomas. Synthesis and Characterization of (Phospine)- and (N-Heterocyclic Carbene)Gold(I) Halides, Azides, Alkynyls, Triazoles, and Dendrimers and the Synthesis and Characterization of Gold(I) Thiacrown Macrocycles. 2011. Case Western Reserve University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=case1282230551.

    MLA Style (8th edition)

  • Robilotto, Thomas. "Synthesis and Characterization of (Phospine)- and (N-Heterocyclic Carbene)Gold(I) Halides, Azides, Alkynyls, Triazoles, and Dendrimers and the Synthesis and Characterization of Gold(I) Thiacrown Macrocycles." Doctoral dissertation, Case Western Reserve University, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=case1282230551

    Chicago Manual of Style (17th edition)