SYNTHESIS AND REACTIVITY STUDIES OF METAL CARBONYL COMPLEXES WITH PYRIDINE/THIONE MIXED-DONOR LIGANDS

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Oian, C. (2015). SYNTHESIS AND REACTIVITY STUDIES OF METAL CARBONYL COMPLEXES WITH PYRIDINE/THIONE MIXED-DONOR LIGANDS. Unc Charlotte Electronic Theses And Dissertations.
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Abstract

A new synthetic route to o (mercaptoimidazolyl)pyridine ligands (R = Me, Bun) through a neutral intermediate o (imidazolyl)pyridine (o-impy) has been developed. The n-butyl-substituted ligand shows improved solubility in organic solvents. The alkyl substituent used does not have a major effect on the amount of electron donation to and from the metal center. The addition of a methylene spacer between pyridine and the imidazole increases the N-M-S bite angle for metal complexes. The coordination chemistry of o (mercaptoimidazolyl)picolines o mpicR (R = Me, Bun) to prepare LMo(CO)4 and LM(CO)3X (M = Mn, X = Br; M = Re, X = Cl, Br) was explored. The group 6 complexes showed low degradation points, which would make them ideal candidates for decomposition to MS2 (M = Mo, W). LRe(CO)5X (X = Cl, Br) complexes were tested for the electrolytic reduction of carbon dioxide by cyclic voltammetry and were able to reduce CO2 to CO.

Details
Author

Oian, Casey

Title

SYNTHESIS AND REACTIVITY STUDIES OF METAL CARBONYL COMPLEXES WITH PYRIDINE/THIONE MIXED-DONOR LIGANDS

Physical Description

1 online resource (118 pages) : PDF

Date

2015

Degree Granting Institution

University of North Carolina at Charlotte

Abstract

A new synthetic route to o (mercaptoimidazolyl)pyridine ligands (R = Me, Bun) through a neutral intermediate o (imidazolyl)pyridine (o-impy) has been developed. The n-butyl-substituted ligand shows improved solubility in organic solvents. The alkyl substituent used does not have a major effect on the amount of electron donation to and from the metal center. The addition of a methylene spacer between pyridine and the imidazole increases the N-M-S bite angle for metal complexes. The coordination chemistry of o (mercaptoimidazolyl)picolines o mpicR (R = Me, Bun) to prepare LMo(CO)4 and LM(CO)3X (M = Mn, X = Br; M = Re, X = Cl, Br) was explored. The group 6 complexes showed low degradation points, which would make them ideal candidates for decomposition to MS2 (M = Mo, W). LRe(CO)5X (X = Cl, Br) complexes were tested for the electrolytic reduction of carbon dioxide by cyclic voltammetry and were able to reduce CO2 to CO.

Genre

masters theses

Subjects--Topics

Chemistry

Degree

M.S.

Keywords

Cabonyl
Carbon Dioxide
Rhenium

Subject Area

Chemistry

Advisor(s)

Rabinovich, Daniel

Committee Members

Jew, Richard
Pando, Miguel
Schmedake, Thomas

Degree Note

Thesis (M.S.)--University of North Carolina at Charlotte, 2015.

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Rights Holder Information

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Identifier

Oian_uncc_0694N_10883

Permalink

http://hdl.handle.net/20.500.13093/etd:1486