Preparation And Characterization Of Meridionally Trischelated Rhenium(i) Terpyridine Dicarbonyl Complexes

Author

Daniel Black

Date of Award

January 2013

Document Type

Thesis

Degree Name

Master of Science (MS)

Department

Chemistry

First Advisor

Sean Hightower

Abstract

Recent work has uncovered a synthetic route to a new series of meridionally coordinated tridentate terpyridine rhenium dicarbonyl complexes. The complex mer,cis-Re(tpy-κ3N)(CO)₂Cl (1) undergoes facile chloride substitution to produce a variety of complexes of the type mer,cis-[Re(tpy-κ3N)(CO)₂(L)]n, where L = CF₃SO₃ (2), CH₃CN (3), CN (4), NC₅H₅ (5), PMe₃ (6), PEt₃ (7), PPh₃ (8), P(OMe)₃ (9), P(OEt)₃ (10), P(OPh)₃ (11) ), P(OiPr)₃ (12), P(OMe)(Ph)₂ (13). Complexes 1-13 absorb light throughout a significant portion of the visible spectrum. The electrochemistry of these compounds is discussed in relation to their observed π-acidity and their ability to significantly stabilize the lower oxidation state of rhenium relative to the tricarbonyl bipyridine systems. The complex mer,cis-Re(tpy-κ3N)(CO)₂Cl (1) produces a first oxidation potential (reversible) that is 0.85 V (vs. SCE) less oxidizing relative to fac-Re(bpy)(CO)₃Cl's first oxidation potential (irreversible).

Recommended Citation

Black, Daniel, "Preparation And Characterization Of Meridionally Trischelated Rhenium(i) Terpyridine Dicarbonyl Complexes" (2013). Theses and Dissertations. 1401.
https://commons.und.edu/theses/1401