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ELECTROCATALYTIC REDUCTION OF ACETYLENE BY MOLYBDENUM-CYSTEINE AND MOLYBDENUM-EDTA COMPLEXES

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Date Issued:
1977
Summary:
Binuclear oxo- and sulfide-bridged Mo(V)-cysteine and Mo(V)-EDTA complexes are chosen as model compounds for nitrogenase enzyme. Both groups of complexes undergo electrochemical reduction in a single four- electron step to Mo(III) dimers. The reduced binuclear Mo (III) units dissociate into catalytically active species capable of reducing the nitrogenase substrate, acetylene. Ease of dissociation increases as oxygen is replaced by sulfur in the bridging unit. Electrocatalytic reduction products of acetylene consist primarily of C2H4 and C2H6 at low partial pressures, but C4H6, C4H8, and higher hydrocarbons predominate at higher pressures. The reduction of substrate is believed to occur by a Mo(III) catalyst adsorbed on the electrode surface. A mechanism is proposed for the e lectrocatalysis, and its relationship to the enzymic catalysis is discussed.
Title: ELECTROCATALYTIC REDUCTION OF ACETYLENE BY MOLYBDENUM-CYSTEINE AND MOLYBDENUM-EDTA COMPLEXES.
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Name(s): LEAZENBEE, LOUIS O.
Florida Atlantic University, Degree grantor
Schultz, Franklin A., Thesis advisor
Charles E. Schmidt College of Science
Department of Chemistry and Biochemistry
Type of Resource: text
Genre: Electronic Thesis Or Dissertation
Issuance: monographic
Date Issued: 1977
Publisher: Florida Atlantic University
Place of Publication: Boca Raton, FL
Physical Form: application/pdf
Extent: 87 p.
Language(s): English
Summary: Binuclear oxo- and sulfide-bridged Mo(V)-cysteine and Mo(V)-EDTA complexes are chosen as model compounds for nitrogenase enzyme. Both groups of complexes undergo electrochemical reduction in a single four- electron step to Mo(III) dimers. The reduced binuclear Mo (III) units dissociate into catalytically active species capable of reducing the nitrogenase substrate, acetylene. Ease of dissociation increases as oxygen is replaced by sulfur in the bridging unit. Electrocatalytic reduction products of acetylene consist primarily of C2H4 and C2H6 at low partial pressures, but C4H6, C4H8, and higher hydrocarbons predominate at higher pressures. The reduction of substrate is believed to occur by a Mo(III) catalyst adsorbed on the electrode surface. A mechanism is proposed for the e lectrocatalysis, and its relationship to the enzymic catalysis is discussed.
Identifier: 13880 (digitool), FADT13880 (IID), fau:10708 (fedora)
Degree granted: Thesis (M.S.)--Florida Atlantic University, 1977.
Collection: FAU Electronic Theses and Dissertations Collection
Note(s): Charles E. Schmidt College of Science
Subject(s): Electrochemical analysis
Enzymatic analysis
Held by: Florida Atlantic University Libraries
Persistent Link to This Record: http://purl.flvc.org/fcla/dt/13880
Sublocation: Digital Library
Use and Reproduction: Copyright © is held by the author with permission granted to Florida Atlantic University to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
Use and Reproduction: http://rightsstatements.org/vocab/InC/1.0/
Host Institution: FAU
Is Part of Series: Florida Atlantic University Digital Library Collections.