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  • Open Daily: 10am - 10pm
    Alley-side Pickup: 10am - 7pm

    3038 Hennepin Ave Minneapolis, MN
    612-822-4611

Open Daily: 10am - 10pm | Alley-side Pickup: 10am - 7pm
3038 Hennepin Ave Minneapolis, MN
612-822-4611
Late-Metal C-H Bond Activation: Cyclopropane Functionalizations and Progress Toward the C-H SIGMA-Bond Complex.

Late-Metal C-H Bond Activation: Cyclopropane Functionalizations and Progress Toward the C-H SIGMA-Bond Complex.

Anstey, Mitchell Ryan

Paperback

Chemistry

Currently unavailable to order

ISBN10: 1243769300
ISBN13: 9781243769305
Publisher: Proquest Umi Dissertation Pub
Pages: 216
Weight: 0.87
Height: 0.46 Width: 7.44 Depth: 9.69
Language: English
Chapter 1. This section presents an overview of the literature pertaining to carbon-hydrogen bond activation. The early discoveries, a delineation between types of C-H bonds activated, mechanisms for the scission of C-H bonds, applications for the formation of value-added molecules, and the relevance for this body of work as it pertains to the author's research program. Chapter 2. Iridium complex Cp*(PMe3)Ir(CH 3)OTf (1) and alkylaminocyclopropanes react via a well-understood initial C--H bond activation with a subsequent C--C bond-breaking step to yield a variety of pi-allyl complexes [Cp*(PMe3)Ir(eta 3-C3H4NR1R2)][OTf] (R1 = R2 = Bn; R1 = Bn, R 2 = Ph) and methane. However, diphenylamino-, alkoxy-, or siloxycyclopropanes, when treated with complex 1, yield a new pi-allyl complex [Cp*(PMe 3)Ir(eta3-C3H4CH3)][OTf] (8) and the corresponding amine or alcohol. The methyl group initially bound to iridium is no longer extruded as methane, but instead is incorporated into the allyl moiety to give a new carbon--carbon bond. A detailed mechanistic study provides evidence in support of an initial C--C bond activation mechanism as opposed to the initial C--H bond activation observed with other known substrates. Chapter 3. Several monometallic rhenium complexes have been synthesized with the intent to investigate their ability to bind alkane C-H sigma-bonds without oxidative cleavage. Each of these complexes contains a 1,2-di- tert-butylcyclopentadiene ligand for the purpose of increasing solubility and at least one photolabile ligand. Studies show that these complexes will release the photolabile ligand upon irradiation, and these new unsaturated complexes can bind to alkanes and traditional ligands such as phosphines and isonitriles. A new apparatus for observing reaction progress by Nuclear Magnetic Resonance spectroscopy during photochemical reactions is outlined. Chapter 4. Several rhenium complexes containing two or three metal centers have been synthesized with the intent to investigate their ability to bind alkane C-H sigma-bonds without oxidative cleavage. The experimental methods are similar to those outlined in Chapter 3. Binding to traditional ligands such as phosphines is reported, but no alkane C-H sigma-bond complexes are observed.

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