Synthesis and reactivity of molybdenum organometallic complexes supported by amide ligands

Chapter 1. Synthesis and Reactivity of Molybdenum Alkyl Complexes Supported by a Diamidoamine Ligand. The synthesis of a new diamidoamine ligand, CH3N[CH2CH2NH(3-(CF3)C6H4)]2 (H2L) is reported. Molybdenum complexes of the type X[LMoC13] (X = Et3NH, Bu4N) are readily synthesized as purple air and moisture sensitive crystalline solids. They may be alkylated by Grignard reagents to yield the monoalkyl complex LMo(Cl)(CH2CMe3), the alkylidyne complex LMo(CCMe3)(CH2CMe3) via a,a - elimination of dihydrogen, and the stable complex LMo(CH2TMS)2 (TMS = SiMe3). LMo(CH2TMS)2 is readily oxidized by cyclohexene sulfide and hexachloroethane to yield, initially, molybdenum alkylidenes that readily undergo decomposition reactions to the bridging sulfide complex {LMoS}2 and [LMo(CTMS)Cl]2, respectively. However, the alkylidene complex LMo(CHTMS)(q2 - MeCCMe) may be isolated if LMo(CH2TMS)2 is heated in the presence of five equivalents of 2-butyne. It is a rare example of an alkylidene and alkyne in the coordination sphere of a group six metal. The relationship between oxidation and alkyne binding is discussed. Chapter 2. Early Transition Metal Pyrrolyl Complexes: Structure, Spectroscopy, Hapticity, and Fluxional Processes.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2007

Author dc:creator

• Hock, Adam S. (Adam Scott)

Advisor dc:contributor.advisor

• Richard R. Schrock.

• Chemistry.

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• 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/1721.1/38624

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/38624