<mods:mods xmlns:mods="http://www.loc.gov/mods/v3" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns:METS="http://www.loc.gov/METS/" ID="etd733" xsi:schemaLocation="http://www.loc.gov/mods/v3 http://www.loc.gov/standards/mods/v3/mods-3-2.xsd">
<mods:titleInfo>
<mods:title>Synthesis and electrochemical study of aromatic manganese carbonyl complexes and applications in hydrogen storage & proton reduction catalysis</mods:title>
</mods:titleInfo>
<mods:name type="personal">
<mods:namePart>Dai, Wei </mods:namePart>
<mods:role>
<mods:roleTerm type="text">creator</mods:roleTerm>
</mods:role>
</mods:name>
<mods:originInfo>
<mods:copyrightDate>2011</mods:copyrightDate>
</mods:originInfo>
<mods:physicalDescription>
<mods:extent>xxx, 172 p.</mods:extent>
<mods:digitalOrigin>born digital</mods:digitalOrigin>
</mods:physicalDescription>
<mods:note>Thesis (Ph.D. -- Brown University (2011)</mods:note>
<mods:name type="personal">
<mods:namePart>Sweigart, Dwight</mods:namePart>
<mods:role>
<mods:roleTerm type="text">Director</mods:roleTerm>
</mods:role>
</mods:name>
<mods:name type="personal">
<mods:namePart>Sun, Shouheng</mods:namePart>
<mods:role>
<mods:roleTerm type="text">Reader</mods:roleTerm>
</mods:role>
</mods:name>
<mods:name type="personal">
<mods:namePart>Kim, Eunsuk</mods:namePart>
<mods:role>
<mods:roleTerm type="text">Reader</mods:roleTerm>
</mods:role>
</mods:name>
<mods:name type="corporate">
<mods:namePart>Brown University. Chemistry</mods:namePart>
<mods:role>
<mods:roleTerm type="text">sponsor</mods:roleTerm>
</mods:role>
</mods:name>
<mods:genre authority="aat">theses</mods:genre>
<mods:subject>
<mods:topic>organometallic</mods:topic>
</mods:subject>
<mods:subject>
<mods:topic>surface modification</mods:topic>
</mods:subject>
<mods:subject>
<mods:topic>heterodinuclear</mods:topic>
</mods:subject>
<mods:subject>
<mods:topic>diazotization</mods:topic>
</mods:subject>
<mods:subject>
<mods:topic>metal hydride</mods:topic>
</mods:subject>
<mods:subject authority="FAST" authorityURI="http://id.worldcat.org/fast" valueURI="http://id.worldcat.org/fast/906358"><mods:topic>Electrocatalysis</mods:topic></mods:subject><mods:subject authority="FAST" authorityURI="http://id.worldcat.org/fast" valueURI="http://id.worldcat.org/fast/906371"><mods:topic>Electrochemistry</mods:topic></mods:subject><mods:subject authority="FAST" authorityURI="http://id.worldcat.org/fast" valueURI="http://id.worldcat.org/fast/1047971"><mods:topic>Organometallic compounds</mods:topic></mods:subject><mods:recordInfo>
<mods:recordContentSource authority="marcorg">RPB</mods:recordContentSource>
<mods:recordCreationDate encoding="iso8601">20111003</mods:recordCreationDate>
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<mods:language><mods:languageTerm type="code" authority="iso639-2b">eng</mods:languageTerm><mods:languageTerm type="text">English</mods:languageTerm></mods:language><mods:abstract>The scope of understanding of aromatic manganese reductive electrochemistry was extended. Five internally connected projects will be introduced. My studies primarily focused on homogeneous and heterogeneous electrochemistry of organomanganese complexes and possible application in electrocatalysis, specifically, proton reduction catalysis. The mechanism of homogeneous reductive electrochemistry of [(η<sup>6</sup>-HMB)Mn(CO)<sub>3</sub>]⁺ was investigated: it undergoes 1-electron irreversible reduction at room temperature and 2-electron reversible reduction at low temperature. And for the first time, we observed reversibility of 2-electron reduction at room temperature by altering the electrochemical environment. An important reduction intermediate [(η<sup>6</sup>-HMB)Mn(CO)<sub>2</sub>]⁻ was believed to catalyze proton reduction in strong acidic condition. The proton coupled reduction mechanism was discussed, based on which, optimization of this new class of Mn-catalyst was also proposed. Followed by a different mechanism, polyarene analog, (η<sup>6</sup>-naphthalene) Mn(CO)<sub>3</sub>⁺ can be used to transfer and store electric energy to stable "metal hydride" complex and releases the hydrogen when needed.A one-step synthetic method for direct synthesis of (η<sup>6</sup>-aniline) manganese tricarbonyl cation and its analogs was discovered. The aniline complex is an important precursor for heterogeneous electrochemistry study. The purpose of heterogeneous electrochemistry study is to achieve the reductive electrochemical reversibility by covalent attachment of electrode surface with arene manganese tricarbonyl moiety. Physical separation of manganese compound may stop the dimerization after one-electron reduction and result in reductive reversibility. One of my projects is focused on covalent attachment of arene manganese tricarbonyl using diazonium-base chemistry and collecting &amp; analyzing e-chem signal from the surface functionalized electrode. The η<sup>6</sup>-aromatic manganese dicarbonyl anion is strong nucleophile. It would be interesting to check the reaction between the manganese anion with [(η<sup>6</sup>-HMB)Re(CO)<sub>3</sub>]PF<sub>6</sub>. We want to explore the possibility of forming the heterodinuclear dimmer with a novel core structure of Mn-Re metal-metal bond. There is no report about the study of Mn-Re metal-metal bond; furthermore, heterodinuclear complex has potential applications in molecular catalysis.</mods:abstract><mods:identifier type="doi">10.7301/Z00V8B2R</mods:identifier><mods:accessCondition type="rights statement" xlink:href="http://rightsstatements.org/vocab/InC/1.0/">In Copyright</mods:accessCondition><mods:accessCondition type="restriction on access">Collection is open for research.</mods:accessCondition><mods:typeOfResource authority="primo">dissertations</mods:typeOfResource></mods:mods>