California State University, Northridge WordmarkOviatt Library WordmarkOviatt Library Catalog Wordmark
Author Ryan, Matthew, author.
Title Synthesis and characterization of new rhodium-carbene and new iron-carbene complexes / by Matthew Ryan.
Published [Northridge, California] : California State University, Northridge, 2013.
 Electronic Book  QD40 .Z95 2013 R93eb    ONLINE
Description 1 online resource (xxv, 402 pages)
Content Type text
Format online resource
File Characteristics text file PDF
Thesis M.S. California State University, Northridge 2013.
Bibliography Includes bibliographical references (pages 193-204).
Access Restricted access; Author's permission required.
Summary Author's group has previously developed a new method for the preparation of ruthenium indenylidene olefin metathesis catalysts. The new method is based on the reaction between ruthenium starting materials and specially designed derivatives of propargyl alcohols (e.g., 1-(3,5-dimethoxyphenyl)-1-phenylprop-2-yn-1-ol). In an effort to study the chemistry of these organic precursors with starting materials of other transition metals, reactions between our propargyl alcohol and [RhCl(PiPr3)2]2 dimer were investigated. These studies led to the synthesis of new rhodium vinylidene, allenylidene and η5-indenyl complexes, which were characterized by 1H, 13C, and 31P NMR spectroscopy and high resolution mass spectrometry. X-ray crystal structures of the vinylidene and η5-indenyl complexes were also obtained. The η5-indenyl complex was obtained by adding HCl(aq) to the vinylidene compound. This represents the first synthesis of a rhodium η5-indenyl complex from a propargyl alcohol precursor. The formation of the η5-indenyl molecule suggests that a rhodium-indenylidene complex was generated along this pathway. However, isolation of any related rhodium indenylidene complex has been elusive. One of the group's long-term goals is to prepare an olefin metathesis catalyst based on iron, an abundant and innocuous transition metal. As a step toward this goal, they decided to test whether our organic precursor can be utilized to synthesize iron indenylidene complexes. Since Fe(CO)2(P(OMe)3)2 is isolobally analogous to a carbene H2C: fragment and since [Fe(CO)2(I)(PR3)2]-Na+ complexes are known to react with propargyl alcohols to afford vinylidene complexes, the reactions between [Fe(CO)2(I)(PR3)2]-Na+ (where R is OMe) and 1-(3,5-dimethoxyphenyl)-1-phenylprop-2-yn-1-ol were studied. Preliminary results related to the characterization of these reactions' products using FT-IR, 1H-, 13C-, and 31P-NMR and in some cases 2D-NMR are presented herein. One of the products is the putative diallenylidene complex Fe(CO)2(PR3)2(allenylidene)2 (where R is OMe). Additional research focused on reactions between [Fe(CO)2(I)(PR3)2]-Na+ and the labeled form of our organic precursor is underway in the group's laboratory.
Note Description based on online resource; title from PDF title page (viewed on February 08, 2013).
Subject Organic compounds -- Synthesis.
Local Subject Dissertations, Academic -- CSUN -- Chemistry and Biochemistry -- Chemistry.
OCLC number 849910397