Controlling the reactivity of Mo(III) with di- and tri-atomic molecules via sterically demanding ligands

Chapter 1. Molybdenum Dinitrogen Chemistry: Formation and Reactivity of (Ar[tBu]N)3MoN2- A collection of (Ar[tBu]N)3MoN2- compounds, supported with Na+, K+, Mg2+ and Ca2+ have been prepared through a variety of synthetic routes. In several experiments, N2 was replaced with other small molecules to produce such complexes as (Ar[tBu]N)3MoCS2- and (Ar[tBu]N)3MoCO-. In most of the experiments examined, N2 was maintained and functionalized as a ligand to create a variety of complexes with the formula (Ar[tBu]N)3MoN2X, where X = Me, Ti(NMe2)3, ZrCp2(Me), GeMe3, SnMe3, AlMe2, ZnMe(THF)2, P(NMe2)2. The functionalized Np with these metal or main-group substituents was shown to have a rather robust bond into which CO2 insertion was not possible. However, the reactivity derived from within a series of carboxydiazenido complexes, (Ar[tBu]N)3MoN2CO2R was strikingly different. The molecule fell apart upon deprotecting the CO2 fragment by removing an alkyl group, unless stabilized with the trimethylsilyl group. Overall, the knowledge gained from this assortment of compounds may be valuable for future dinitrogen chemistry of (Ar[tBu]N)3Mo or other dinitrogen complexes in general. Chapter 2. A di-Molybdenum gu-N Compound as a Reactive Precursor and a Gateway into N2 Chemistry of (Ar['Pr]N)3Mo and (AdO)3Mo ((Ar['Pr]N)3Mo )2(1 -N) was investigated electrochemically as well as synthetically. The anion and cation were both synthesized and investigated as [Na(THF)x][ ( (Ar['Pr]N)3Mo 12(I-N )] and [( (Ar['Pr]N)3Mo 12(-N) ][OTf], respectively. The triflate salt was isolated as a stable complex whereas the sodium salt was characterized in situ.

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2002

Author dc:creator

• Cherry, John-Paul F. (John-Paul Francis), 1971-

Advisor dc:contributor.advisor

• Christopher C. Cummins.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

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

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/8366

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/8366