Oxygen atom transfer with manganese-exchanged metal-organic frameworks

Oxygenates represent some of the most versatile commodity chemicals, justifying continued interest in the discovery of new selective oxidation catalysts from both a fundamental and applied perspective. Metal-organic frameworks (MOFs) are an attractive platform for catalysis because they enable access to unique coordination environments and reactivities; this is due in part to their tunability combined with the site isolation offered by their solid state. In one example, partial substitution of Zn[superscript II] by Mn[superscript II] in Zn₄O(terephthalate)₃ (MOF-5) leads to a distorted all-oxygen ligand field supporting a single Mn[superscript II] site, whose structure was confirmed by Mn K-edge X-ray absorption spectroscopy. Upon exposure to [superscript t]BuSO₂PhIO, Mn-MOF-5 produces a putative Mn[superscript IV]-oxo intermediate, which upon further reaction with adventitious hydrogen is trapped as a Mn[superscript III]-OH species.

Name thesis:degree_name

Doctoral

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2019

Author dc:creator

• Stubbs, Amanda Walcott.

Advisor dc:contributor.advisor

• Mircea Dincă.

• Chemistry.

Statement dc:rights

• MIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

https://hdl.handle.net/1721.1/124054

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/124054